Substituted 4-(2-benzothiazolyl)phenylazo dyes having a quaternary ammonium, hydrazinium or optionally substituted amino substituent

ABSTRACT

Azo dyes of the formula ##SPC1## 
     Where 
     X stands for the radical of a coupling component of the aminobenzene, hydroxybenzene, aminonaphthalene, hydroxynaphthalene or heterocyclic series or one with a coupling methylene group, 
     A n   -  for an anion equivalent to K n   + , 
     n for 1 to 6, 
     K +  for the group ##EQU1## and where the aromatic rings B and/or D may be further substituted. The dyes are useful for dyeing and printing paper (e.g., dyeing in the stock). The dyed paper is fast to light and wet treatments and has good fastness to bleaching, water, alcohol and light.

This application is a continuation of application Ser. No. 790,903, filed Jan. 10, 1969, and now abandoned.

This invention relates to a process for the dyeing and printing of paper, using for this purpose azo dyes of the formula ##EQU2## where X stands for the radical of a coupling component of the aminobenzene, hydroxybenzene, aminonaphthalene, hydroxynaphthalene or heterocyclic series or one with a coupling methylene group,

A_(n) ⁻ for an anion equivalent to K_(n) ⁺,

N for 1 to 6,

K⁺ for the group ##EQU3## and where the aromatic rings B and/or D may be further substituted.

In formulae (II) and (III)

R₁ stands for an alkyl or cycloalkyl radical which may be substituted, or jointly with R₂ and the adjacent N atom for a heterocycle,

R₂ for an alkyl or cycloalkyl radical which may be substituted, or jointly with R₁ and the adjacent N atom for a heterocycle,

R₃ and R₄ stand for hydrogen atoms or identical or different alkyl or cycloalkyl radicals which may be substituted or identical or different acyl radicals,

R₅ stands for a hydrogen atom or an alkyl, aryl or cycloalkyl radical which may be substituted,

R₆ for a hydrogen atom or an alkyl, aryl or cycloalkyl radical which may be substituted,

R₇ for a hydrogen atom or an alkyl or cycloalkyl radical, which may be substituted, and

R₁ together with R₃ and/or R₂ together with R₄, together with the N atoms adjacent to the substituents, and

R₅ and R₆ or

R₅, r₆ and R₇ together with the adjacent N atoms may form heterocycles.

This invention relates further to azo dyes of the formula ##EQU4## where X stands for the radical of a coupling component of the aminobenzene, hydroxybenzene, aminonaphthalene, hydroxynaphthalene or heterocyclic series or one with a coupling methylene group,

A_(n) ⁻ for an anion equivalent to (K'₁ ⁺)_(n),

n for 1 to 6,

K'₁ ⁺ for the group ##EQU5## and where the aromatic rings B and/or D may be further substituted.

In formulae (II) and (V)

R₁ stands for an alkyl or cycloalkyl radical, which may be substituted, or jointly with R₂ and the adjacent N atom for a heterocycle,

R₂ for an alkyl or cycloalkyl radical which may be substituted, or jointly with R₁ and the adjacent N atom for a heterocycle,

R₃ and R₄ stand for hydrogen atoms or identical or different alkyl or cycloalkyl radicals, which may be substituted or identical or different acyl radicals,

R₈, r₉ and R₁₀ stand for alkyl or cycloalkyl radicals, which may be substituted,

and where R₁ together with R₃ and/or R₂ together with R₄ and the N atoms adjacent to these substituents,

and R₈ and R₉ or

R₈, r₉ and R₁₀ together with the adjacent N atom may form heterocycles.

This invention relates further to azo dyes of the formula ##EQU6## where X represents the radical of a coupling component of the aminobenzene, hydroxybenzene, aminonaphthalene, hydroxynaphthalene or heterocyclic series or one with a coupling methylene group,

n 1 to 6,

and R₁₁ and R₁₂ each represents a hydrogen atom or an alkyl, aryl or cycloalkyl radical which may be substituted,

and where the aromatic rings B and/or D may be further substituted,

and the radicals R₁₁ and R₁₂, jointly with the adjacent N atom, may form a saturated or partially saturated heterocycle.

The dyes of formula (IV) can be produced, for example, by reacting one mole of a compound of the formula ##EQU7## where A represents a radical convertible into an anion, with n moles of the compound of the formula ##EQU8##

The dyes of formula (VI) can be produced, for example, by reacting 1 mole of a compound of the formula ##EQU9## where A₁ represents the acid radical of an ester, with n moles of a compound of formula ##EQU10##

Particularly good dyes are of the formula ##EQU11## where m represents 1 to 3

and A_(m) ⁻ an anion equivalent to K'_(1m) ⁺.

The dyes of formula (XII) can be produced, for example, by coupling the diazo compound of an amine of the formula ##EQU12## with a coupling component of the formula

H -- X (XIV).

Equally good dyes are those of the formula ##EQU13## where X₁ stands for the radical of a coupling component of the aminobenzene, hydroxybenzene, heterocyclic, aminonaphthalene or hydroxynaphthalene series, or one with a coupling methylene group,

Y for the direct linkage or a divalent bridge member,

p for 0 to 3

and A⁻ for an anion.

The dyes of formula (XV) can be produced, for example, by coupling the diazo compound of an amine of the formula ##EQU14## with a coupling component of the formula

H -- X₁ -- Y -- K'₁ A⁻ (XVI).

Similarly good dyes correspond to the formula ##EQU15## where m represents 1 to 3.

The dyes of formula (XVII) are produced by coupling the diazo component of an amine of the formula ##EQU16## with a coupling component of the formula

H -- X (XIV).

equally good dyes correspond to the formula ##EQU17## The dyes of formula (XIX) can be obtained by coupling a diazo component of an amine of formula (XVIII) with a coupling component of the formula ##EQU18## Compounds of formula (VII) can be obtained by reacting 1 mole of a compound of the formula ##EQU19## with n moles of halomethane. Compounds of the formula ##EQU20## can be obtained by reacting 1 mole of a compound of the formula with n moles of halomethane.

In the compounds of formulae (I), (IV), (XII), (XIII), (XIIIa) and (XV) the anion A⁻ can be exchanged for other anions, e.g. with the aid of an ion exchanger or by reaction with salts or acids, if required in more than one stage, e.g. via the hydroxide.

Particularly good dyes are obtained when the radicals R₃ and R₄ stand for hydrogen atoms or when the radicals R₁ and R₂ and R₅ to R₇ or R₈ to R₁₀ each represents a lower alkyl radical, containing e.g. 1 to 3 carbon atoms, which may be substituted or when R₁₁ represents a preferably lower alkyl radical, containing e.g. 1 to 3 carbon atoms, which may be substituted and R₁₂ hydrogen or when the radicals R₁₁ and R₁₂ represent preferably lower alkyl radicals, containing e.g. 1 to 3 carbon atoms, which may be substituted. Halogen represents preferably chlorine or bromine.

When R₃ and R₄ do not stand for hydrogen atoms or acyl radicals and R₅, R₆, R₁₁ and R₁₂ do not stand for hydrogen atoms or aryl radicals and R₇ does not stand for a hydrogen atom, the radicals R₁ to R₁₂ represent unsubstituted or substituted methyl, ethyl, propyl, butyl, cycloalkyl, e.g. cyclohexyl, or benzyl radicals. If these radicals are substituted they contain in particular a hydroxyl group, a halogen atom or a cyano group.

The radicals R₅, R₆, R₁₁ and R₁₂ may alternatively stand for an aryl radical which may be substituted, such as phenyl, naphthyl or tetrahydronaphthyl radical. Examples of substituents for the aryl radicals are alkyl, alkoxy, halogen, cyano, nitro, hydroxyl and substituted or unsubstituted amino groups.

The radicals R₁ and R₂ and R₁₁ and R₁₂, together with the adjacent N atom, may form a heterocycle, for example a saturated or partly saturated heterocycle, e.g. a pyrrolidine, piperazine, morpholine, pyridine or piperidine ring.

The radical R₁ together with R₃ and/or the radical R₂ together with R₄ and the N atoms adjacent to these substituents may form a saturated or unsaturated, preferably five- or six-membered heterocycle, for example a pyrazolidine, pyridazine or pyrazoline ring, e.g. a trimethylenepyrazolidine or tetramethylenepyrazolidine ring.

The acyl radicals R₃ and R₄ are preferably of formula R₂₀ --SO₂ -- or R₂₁ --CO--, where R₂₀ stands for an aromatic or saturated or unsaturated aliphatic or cycloaliphatic radical and R₂₁ for hydrogen or R₂₀. The two acyl radicals may form a ring with the adjacent N atom. R₂₀ or R₂₁ may represent, e.g. formyl, acetyl, propionyl, butyroyl, acryloyl, cyanoacetyl, benzoyl, methylsulphonyl, substituted or unsubstituted phenylsulphonyl.

The radicals R₅ and R₆ and R₈ and R₉, together with the adjacent N atom, may form a heterocycle, for example a pyrrolidine, piperidine, morpholine, aziridine or piperazine ring. The radicals R₅, R₆ and R₇ or R₈, R₉ and R₁₀, together with the adjacent N atom, may form a heterocycle, e.g. a group of the formula ##EQU21## or may stand for a pyridine ring.

The rings B and/or D may be further substituted, preferably by non-water-solubilizing substituents. They contain preferably lower alkyl or alkoxy groups, containing e.g. 1 to 3 carbon atoms, or hydroxyaryl or alkoxyaryl groups.

The dyes of formulae (I), (IV), (VI), (XII), (XV), (XVII) and (XIX) may contain further a sulpho, carboxy, sulfamoyl, carbamoyl, alkylsulfonyl or arylsulfonyl group.

The anion A⁻ may be an organic or inorganic ion, e.g. a halogen ion such as that of chloride, bromide or iodide, the ion of methylsulphate, sulphate, disulphate, perchlorate, phosphotungstate, phosphotungstic molybdate, benzenesulphonate, naphthalenesulphonate, 4-chlorobenzenesulphonate, oxalate, maleinate, acetate, propionate, methanesulphonate, chloroacetate or benzoate, or a complex anion such as that of zinc chloride double salts.

The coupling components and/or aromatic rings B and/or D in the compounds of formulae (I), (IV), (XII) and (XV) may bear, besides a group -K⁺ or -K₁ ⁺, other cationic groups different from the aforenamed, e.g. ammonium, hydrazinium or cycloimmonium groups. The coupling components include, for example, those of the aromatic series, e.g. the benzene and naphthalene series, which bear one substituent capable of coupling, e.g. aminobenzenes, hydroxybenzenes, aminonaphthalenes and hydroxynaphthalenes; further, coupling components of the heterocyclic series such as the pyrazolone, quinoline, hydroxyquinoline and tetrahydroquinoline series, the aminopyrazole, indole and carbazole series, e.g. 1-phenyl-3-methyl-pyrazolone-5 and its derivatives, and compounds having a coupling methylene group, e.g. acylacetic acid alkyl and aryl amides, e.g. acetoacetylaminoalkyl amides and acetoacetylaminophenyl amides.

Examples of suitable components are 1-hydroxy-4-methylbenzene, 1,3-dihydroxybenzene, 2-hydroxynaphthalene, 1-hydroxy-4-methoxynaphthalene, 2-hydroxy-8-acetylamino- and 8-methylsulphonylaminonaphthalene, 1-hydroxy-6- and -7-amino-, -methylamino-, -phenylamino-, -(4'-methoxyphenylamino)-, -(2',4',6'-trimethylphenylamino)-naphthalene, aromatic compounds with one primary or secondary amino group such as aminobenzene and its derivative, 1,3-diaminobenzene, 1-aminonaphthalene, 2-amino-, 2-phenylamino- or 2-methylamino-5-hydroxynaphthalene; acetoacetylaminobenzenes, 1-acetoacetylamino-2-ethylhexane, 1-acetoacetylaminobutane, barbituric acid, 1-(3'-chlorophenyl)-3-methyl-5-pyrazolone, 1-(3'-cyanophenyl)-3-methyl-5-pyrazolone.

The preferred substituents in these compounds are non-water-solubilizing substituents such as those which occur in known dyes of acetate and polyester fibres. Special suitable substituents are halogen such as chlorine, bromine and fluorine, nitrile, nitro, alkyl, alkoxy, trihaloalkyl, alkylsulphonyl, sulphonamide, e.g. mono- and di-alkylsulphonamide, carbalkoxy (alkexycarbonyl), carboxylic acid amide and hydroxyl groups and arylazo groups such as azophenyl, azodiphenyl and azonaphthyl groups.

These compounds may however contain water-solubilizing substituents, e.g. sulphonic acid, sulphonic acid amide, carboxylic acid or carboxylic acid amide groups.

Y stands for the direct linkage or a divalent bridge member, which may be attached through a carbon atom to K⁺ or K₁ ⁺. The divalent bridge member may be an unsubstituted or substituted, straight or branched alkylene radical which may bear 1 to 12 or preferably 1 to 4 carbon atoms and may be interrupted by heteroatoms or groups of hetero atoms. It may alternatively stand for an unsubstituted or substituted arylene radical, e.g. a phenylene radical, or for an alkylene-phenylene or phenylene-alkylene radical.

Examples of hetero atoms and groups of hetero atoms are ##EQU22## --O--, --S--, ##EQU23## or ##EQU24## where R represents a hydrogen atom or an unsubstituted or substituted hydrocarbon radical, e.g. an alkyl radical.

Y may be, for example, --(CH₂)_(p) --, where p represents a number from 1 to 6, ##EQU25## --NH--CO--CH₂ --, --NH--CO--C₂ H₄ --, --O--CH₂ --, --O--C₃ H₆ --, --CO--CH₂ --, --O--C₂ H₄ --, --CO--NH--CH₂ --, --CO--NH--C₃ H₆ --, --SO₂ --C₂ H₄ --, ##EQU26## --NH--CH₂ --CHOH--CH₂ --, ##EQU27## --CH₂ --CHOH--CH₂ --, --CH₂ --NH--CO--CH₂ --, --CH₂ --CO--NH--CH₂ --, etc.

The alkyl and alkoxy radicals usually contain 1 to 12 or 1 to 6 or preferably 1 to 4 carbon atoms. They may be straight or branched and may be substituted, e.g. by the hydroxyl or cyano group or by halogen atoms.

The reaction of a compound of formula (VII) or a compound of the formula ##EQU28## with a compound of formula (VIII) or (IX) to form a compound of formula (IV) or (XII) respectively is conducted preferably in water and at temperatures of -10°C to +100°C, advantageously at 20° to 50°C.

The reaction can be carried out in an organic solvent with or without the addition of water or in the absence of solvent at temperatures of -10° to 180°C, advantageously at 20° to 120°C.

Under the same conditions a compound of formula (X) or of the formula ##EQU29## can be reacted with a compound of formula (XI) to give a compound of formula (VI) or (XVII) respectively.

The coupling reaction is effected by the known methods. The radicals A convertible into an anion and the acid radicals A₁ of esters are preferably those of hydrohalic acids; A or A₁ stands preferably for Cl or Br; further radicals A and A₁ are, for example, those of sulphuric acid, a sulphonic acid or of hydrogen sulphide.

The dye of the formula ##EQU30## is known from British Pat. 576,270 for the dyeing of cellulosic fibres, whilst the dye of the formula ##EQU31## in known from French Pat. 1,495,232 and Belgian Patent 633,447 for the dyeing of paper.

It was surprising that the dyes of formulae (I), (IV) and (VI), can be discharged better with chlorine when dyed on paper are useful for dyeing and printing paper. Paper can be dyed by the normal methods. The dyeings on paper are fast to light and wet treatments and have good fastness to bleaching, water, alcohol and light. Mixture of two or more of the new dyes or mixtures of them and other cationic dyes can be employed advantageously. The dyes of this application are well-soluble in water and have good pH stability and good built-up power.

In the following Examples the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1

24 Parts of 2-(4'-aminophenyl)-6-methylbenzothiazole are diazotized in hydrochloric acid solution with 7 parts of sodium nitrite. The diazonium salt solution is coupled with 15 parts of 2-hydroxynaphthalene in acetic acid solution. A red dye is formed which is dissolved in a mixture of 100 parts of chclorsulphonic acid and 35 parts of sulphuric acid, and to this solution 20 parts of paraformaldehyde are added. The solution is stirred in 300 parts of water and 100 parts of 40% aqueous trimethylamine solution for 10 hours at 40°. A water soluble red dye is obtained.

EXAMPLE 2

a. 24 Parts of 2-(4'-aminophenyl)-6-methylbenzothiazole and 20 parts of paraformaldehyde are entered into a mixture of 100 parts of chlorosulphonic acid and 35 parts of sulphuric acid. The mixture is stirred for 10 hours at 60°. The chloromethylated product is obtained.

b. 29 Parts of the chloromethylated 2-(4'-aminophenyl)-6-methylbenzothiazole are dissolved in 300 parts of water and 50 parts of a 40% aqueous trimethylamine solution. The solution is stirred for 4 hours at 40°, on which the corresponding trimethylammonium compound is obtained which is readily soluble in water.

c. This compound is diazotized with 7.2 parts of sodium nitrite in hydrochloric acid solution and coupled with 22 parts of acetoacetic acid anisidide in acetic acid solution. A greenish yellow dye is obtained.

EXAMPLE 3

The diazonium compound according to step b) of Example 2 is coupled with 18 parts of 1-phenyl-3-methylpyrazolone-5 in acetic acid solution to give an orange-yellow dye.

EXAMPLE 4

A dye identical with that of Example 1 is obtained when the diazonium compound of Example 2b) is coupled with 15 parts of 2-hydroxynaphthalene.

EXAMPLE 5

The chloromethylated compound obtained in Example 2 (a) is reacted with an aqueous solution of asymmetrical dimethylhydrazine for the formation of the corresponding dimethylhydrazinium compound.

The diazo compound of the dimethylhydrazinium compound thus obtained is coupled with 2-hydroxynaphthalene to give a red dye similar to that of Example 1.

DYEING EXAMPLE A

0.2 Parts of the dye of Example 1 or 6 are dissolved in water or in a mixture of water and acetic acid and the solution is stirred into paper stock consisting of 70 parts of chemically bleached sulphite cellulose and 30 parts of chemically bleached birch cellulose. After 10 minutes the stock is fabricated into absorbent paper which is dyed in a wet-fast red shade.

DYEING EXAMPLE B

100 Parts of chemically bleached sulphite cellulose are refined in a beater, during which operation 2 parts of rosin size and shortly afterwards 0.5 parts of an aqueous or aqueous-acetic acid solution of the dye of Example 1 or 6 are added. After 10 minutes 3 parts of aluminum sulphate are added and after a further 10 minutes the stock is converted into paper. The paper is dyed in a bright red shade of medium depth which is light- and wet-fast.

EXAMPLE 6

24 Parts of 2-(4'-aminophenyl)-6-methylbenzothiazole are diazotized in hydrochloric acid solution with 7 parts of sodium nitrite. The diazonium salt solution is coupled with 15 parts of 2-hydroxynaphthalene in acetic acid solution. A red dye is obtained.

The dye is dissolved in a mixture of 100 parts of chlorosulphonic acid and 35 parts of sulphuric acid and the solution mixed with 20 parts of paraformaldehyde. After stirring for 12 hours at 60° the chloromethylated dye is obtained. The dye is dissolved in a solution of 240 parts of 40% aqueous dimethylamine solution and 10 parts of sodium carbonate in 200 parts of water, with subsequent stirring at 40° for 5 hours. The product is a red dye which is soluble in a mixture of water and acetic acid.

EXAMPLE 7

The following procedure yields the same dye as that of Example 6. 24 Parts of 2-(4'-aminophenyl)-6-methylbenzothiazole and 20 parts of paraformaldehyde are entered into a mixture of 100 parts of chlorosulphonic acid and 35 parts of sulphuric acid. The mixture is stirred for 10 hours at 60°, on which the chloromethylated product is obtained.

The chloromethylated product is dissolved in a solution of 240 parts of a 40% aqueous dimethylamine solution and 10 parts of sodium carbonate in 300 parts of water and the resulting solution stirred for 5 hours at 40°. The corresponding dimethylamine compound is formed.

The dimethylamine compound is diazotized with sodium nitrite in hydrochloric acid solution and coupled with 2-hydroxynaphthalene in acetic acid solution.

EXAMPLE 8

24 Parts of 2-(4'-aminophenyl)-6-methylbenzothiazole are diazotized with 7 parts of sodium nitrite in hydrochloric acid solution and coupled with 34.3 parts of acetoacetic acid-2-methoxy-5-trimethylammonium-methylene-anilide in acetic acid solution. A water soluble dye of the formula ##EQU32## is obtained, which dyes paper in greenish yellow shades. The coupling component can be produced by the known method. Ortho-nitroanisole is chloromethylated and quaternated with trimethylamine, the nitro group is reduced by the Bechamp reaction and diketene is added.

EXAMPLE 9

24 Parts of 2-(4'-aminophenyl)-6-methylbenzothiazole are diazotized with 7 parts of sodium nitrite in hydrochloric acid solution and coupled with 41 parts of para-(beta-N-ethyl-N-phenylaminoethoxy)-phenyl-trimethylammonium chloride in acetic acid solution. A water soluble dye of the formula ##EQU33## is obtained, which dyes paper in orange-yellow shades.

EXAMPLE 10

24 Parts of 2-(4'-aminophenyl)-6-methylbenzothiazole are diazotized in hydrochloric acid solution with 7 parts of sodium nitrite and coupled with 29 parts of acetoacetic acid-2-methoxy-5-dimethylaminomethylanilide in acetic acid solution. A dye is formed which has the formula ##EQU34## and dyes paper in greenish yellow shades.

The coupling component is prepared by the known method. Ortho-nitroanisole is chloromethylated and the chloromethyl group reacted with dimethylamine, the nitro group is reduced by the Bechamp reaction and diketene added.

EXAMPLE 11

24 Parts of 2-(4'-aminophenyl)-6-methylbenzothiazole are diazotized in hydrochloric acid solution with 7 parts of sodium nitrite and coupled with 38 parts of para-(β-N-ethyl-M-phenylaminoethoxy)-phenyl-dimethylamine to yield a dye of the formula ##EQU35## which gives dyeings of orange-yellow shade on paper.

Table I sets forth the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula: ##SPC2##

where B₁ to B₆ have the meanings given them in Table I. The anion A⁻ may be any one of those named in the description of the process. The symbol K⁺ may stand for any one of the radicals K₁ to K₂₇ listed in Table A below. These groupings may be exchanged in any given dye for another of the stated groupings. The grouping --CH₂ --K⁺ may occur once or twice or preferably one and a half times in the dehydrotoluidine radical shown in square brackets; this grouping occupies preferably the 7 and/or 2' position.

                  Table A                                                          ______________________________________                                         K.sup.+ may stand for any one of the radicals K.sub.1 to K.sub.27 which        represent the following groupings:                                             K.sub.1                                                                               represents                                                                               --N(CH.sub.3).sub.3                                                                              .sup.+                                      K.sub.2                                                                               "         --N(C.sub.2 H.sub.5).sub.3                                                                       .sup.+                                                       CH                .sup.+                                                       |                                                    K.sub.3                                                                               "         --N(C.sub.2 H.sub.5).sub.2                                                     C.sub.2 H.sub.5   .sup.+                                                       |                                                    K.sub.4                                                                               "         --N(CH.sub.3).sub.2                                           K.sub.5                                                                               "         --N(Ch.sub.2 H.sub.4 OH).sub.3                                                                   .sup.+                                                       CH.sub.3          .sup.+                                                       |                                                    K.sub.6                                                                               "         --N(C.sub.2 H.sub.4 OH).sub.2                                                  CH.sub.3          .sup.+                                                       |                                                    K.sub.7                                                                               "         --N--CH.sub.2 OH                                                               |                                                                     C.sub.2 H.sub.5                                                                C.sub.2 H.sub.4 --CONH.sub.2                                                                     .sup.+                                                       |                                                    K.sub.8                                                                               "         --N(CH.sub.3).sub.2                                                            (CH.sub.3).sub.2  .sup.+                                                       |                                                    K.sub.9                                                                               "         --N(C.sub.2 H.sub.4 OH)                                       K.sub.10                                                                              "                           .sup.+                                      K.sub.11                                                                              "                           .sup.+                                                       |                                                                     CH.sub.3                                                      K.sub.12                                                                              "                           .sup.+                                                       |                                                                     CH.sub.3                                                      K.sub.13                                                                              "                           .sup.+                                                       |                                                                     CH.sub.3                                                      K.sub.14                                                                              "                           .sup.+                                                       |                                                                     C.sub.2 H.sub.4 --CONH.sub.2                                  K.sub.15                                                                              "                           .sup.+                                                       |                                                                     C.sub.2 H.sub.4 --CONH.sub.2                                  K.sub.16                                                                              "                           .sup.+                                                       |                                                                     C.sub.2 H.sub.4 --CONH.sub.2                                                   CH.sub.3          .sup.+                                                       |                                                    K.sub.17                                                                              "                                                                       K.sub.18                                                                              "                           .sup.+                                      K.sub.19                                                                              "         --N(CH.sub.3).sub.2                                                                              .sup.+                                                       |                                                                     NH.sub.2                                                      K.sub.20                                                                              "         --N(C.sub.2 H.sub.5).sub.2                                                                       .sup.+                                                       |                                                                     NH.sub.2                                                      K.sub.21                                                                              "         --N(C.sub.2 H.sub.4 OH).sub.2                                                                    .sup.+                                                       |                                                                     NH.sub.2                                                      K.sub.22                                                                              "                           .sup.+                                                       |                                                                     NH                                                            K.sub.23                                                                              "                           .sup.+                                                       |                                                                     NH.sub.2                                                      K.sub.24                                                                              "                           .sup.+                                                       |                                                                     NH.sub.2                                                      K.sub.25                                                                              "         --N(C.sub.2 H.sub.4 --CONH.sub.2).sub.2                                                          .sup.+                                                       |                                                                     NH.sub.2                                                      K.sub.26                                                                              "         --N(C.sub.2 H.sub.4 ON).sub.2                                                                    .sup.+                                                       |                                                                     NH.sub.2                                                                       CH                                                                             CH.sub.2 ∠CH.sub.2                                                                         .sup.+                                                       ||                                          K.sub.27                                                                              "         --NN                                                                           ||                                                           CH.sub. 2 ∠CH.sub.2                                                      CH.sub.2                                                      ______________________________________                                    

                                      Table I                                      __________________________________________________________________________                                                                Shade                                                                          of                  Ex.                                                        dyeing              No.                                                                               K   B.sub.1                                                                           B.sub.2                                                                            B.sub.3                                                                            B.sub.4        B.sub.5           B.sub.6 on                                                                             paper               __________________________________________________________________________     12 K.sub.2                                                                            H  CH.sub.3                                                                           H   H              H                 OH      red                 13 K.sub.3                                                                            H  do. H   H              H                 OH      do.                 14 K.sub.4                                                                            H  do. H   H              H                 OH      do.                 15 K.sub.5                                                                            H  do. H   H              H                 OH      do.                 16 K.sub.6                                                                            H  do. H   H              H                 OH      do.                 17 K.sub.7                                                                            H  do. H   H              H                 OH      do.                 18 K.sub.8                                                                            H  do. H   H              H                 OH      do.                 19 K.sub.9                                                                            H  do. H   H              H                 OH      do.                 20 K.sub.10                                                                           H  do. H   H              H                 OH      do.                 21 K.sub.11                                                                           H  do. H   H              H                 OH      do.                 22 K.sub.12                                                                           H  do. H   H              H                 OH      do.                 23 K.sub.13                                                                           H  do. H   H              H                 OH      do.                 24 K.sub.14                                                                           H  do. H   H              H                 OH      do.                 25 K.sub.15                                                                           H  do. H   H              H                 OH      do.                 26 K.sub.16                                                                           H  do. H   H              H                 OH      do.                 27 K.sub.17                                                                           H  do. H   H              H                 OH      do.                 28 K.sub.18                                                                           H  do. H   H              H                 OH      do.                 29 K.sub.19                                                                           H  do. H   H              H                 OH      do.                 30 K.sub.20                                                                           H  do. H   H              H                 OH      do.                 31 K.sub.21                                                                           H  do. H   H              H                 OH      do.                 32 K.sub.22                                                                           H  do. H   H              H                 OH      do.                 33 K.sub.23                                                                           H  do. H   H              H                 OH      do.                 34 K.sub.24                                                                           H  do. H   H              H                 OH      do.                 35 K.sub.25                                                                           H  CH.sub.3                                                                           H   H              H                 OH      do.                 36 K.sub.26                                                                           H  do. H   H              H                 OH      do.                 37 K.sub.27                                                                           H  do. H   H              H                 OH      do.                 38 K.sub.1 -K.sub.27                                                                  H  do. H   H              --CO--CH.sub.3    OH      do.                 39 do. H  do. H   H              --CO--NH----CO--C.sub.2 H.sub.4 --K.sub.1                                      1                 OH      do.                 40 do. H  do. H   H              --CO--NH--C.sub.2 H.sub.5                                                                        OH      do.                 41 do. H  do. H   OH             H                 H       do.                 42 do. H  do. H   OH             --CO--C.sub.2 H.sub.4 --K.sub.1                                                                  H       do.                                   CH.sub.3                                                                       |                                                   43 do. H  do. H   --SO.sub.2 --NH=CH--C.sub.3 H.sub.6 --K.sub.1                                                 H                 OH      do.                 44 do. H  do. H   H              --CO--NH'C.sub.2 H.sub.4 --K.sub.1                                                               OH      do.                 45 do. H  do. H   H              --CO--NH--CH.sub.2 --CH--CH.sub.2                                              --K.sub.1         OH      do.                                                  |                                                                     CH                                            46 do. H  do. H   --NH--C.sub.2 H.sub.4 --OH                                                                    H                 H       do.                 47 do. H  do. H   --N(CH.sub.3).sub.2                                                                           H                 OH      do.                 48 do. H  do. H   do.            H                 --NH.sub.2                                                                             do.                 49 do. H  do. H   do.            H                 --NH--C.sub.2 H.sub.4                                                          --OH    do.                 50 do. H  do. H   do.            H                 --NH--CH.sub.3                                                                         do.                 51 do. H  do. H   do.            H                 --NH--C.sub.6 H.sub.5                                                                  do.                 52 do. H  do. H   Br             H                 --NH.sub.2                                                                             do.                 53 do. H  do. H   Cl             H                 --NH.sub.2                                                                             do.                 54 do. H  do. H   CH.sub.3       H                 --NH.sub.2                                                                             do.                 55 do. H  do. CH.sub.3                                                                           H              H                 --NH.sub.2                                                                             do.                 56 do. H  CH.sub.3                                                                           OCH.sub.3                                                                          H              H                 --NH.sub.2                                                                             do.                 57 do. H  do. H   --OCH.sub.3    H                 --NH.sub.2                                                                             do.                 58 do. H  do. H   --NH--C.sub.2 H.sub.4 --K.sub.1                                                               H                 H       do.                 59 do. H  do. H   --O--CO--CH.sub.2 --K.sub.1                                                                   H                 H       do.                                   C.sub.2 H.sub.5                                              60 do. H  do. H   --N∠     H                 H       do.                                   CH.sub.2 --CH--CH.sub.2 --K                                                    |                                                                     OH                                                           61 do. H  do. H   --SO.sub.2 --N(CH.sub.3).sub.2                                                                H                 H       do.                 62 do. H  do. H   H              --COOC.sub.2 H.sub.4 --K.sub.1                                                                   OH      do.                 63 do. H  do. H   H              --COOCH.sub.3     OH      do.                 64 do. CH.sub.3                                                                          do. H   H              H                 OH      do.                 65 do. do.                                                                               do. H   H              --CO--CH.sub.3    OH      do.                 66 do. do.                                                                               do. H   H              --CO--NH----CO--C.sub.2 H.sub.4 --K.sub.1                                      4                 OH      do.                 67 do. do.                                                                               do. H   H              --CO--NH--C.sub.6 H.sub.5                                                                        OH      do.                 68 do. do.                                                                               do. H   OH             H                 H       do.                 69 do. do.                                                                               do. H   OH             --CO--C.sub.2 H.sub.4 --K.sub.1                                                                  H       do.                                   CH.sub.3                                                                       |                                                   70 do. do.                                                                               do. H   --SO.sub.2 --NH--CH--C.sub.3 H.sub.6 --K.sub.1                                                H                 OH      do.                 71 do. do.                                                                               do. H   --NH--C.sub.2 H.sub.4 --OH                                                                    H                 H       do.                 72 do. do.                                                                               do. H   H              --CO--NH--C.sub.2 H.sub.4 --K.sub.1                                                              OH      do.                                                  OH                                                                             |                                    73 do. do.                                                                               do. H   H              --CO--NH--CH.sub.2 --CH--CH.sub.2                                              --K.sub.1         OH      do.                 74 do. do.                                                                               do. H   --N(CH.sub.3).sub.2                                                                           H                 H       do.                 75 do. do.                                                                               do. H   --N(CH.sub.3).sub. 2                                                                          H                 --NH.sub.2                                                                             do.                 76 do. do.                                                                               do. H   do.            H                 --NH--C.sub.2 H.sub.4                                                          --OH    do.                 77 do. do.                                                                               do. H   do.            H                 --NH--CH.sub.3                                                                         do.                 78 do. do.                                                                               do. H   do.            H                 --NH--C.sub.6 H.sub.5                                                                  do.                 79 do. do.                                                                               do. H   Br             H                 --NH.sub.2                                                                             do.                 80 do. do.                                                                               do. H   Cl             H                 --NH.sub.2                                                                             do.                 81 do. do.                                                                               do. H   CH.sub.3       H                 --NH.sub.2                                                                             do.                 82 do. do.                                                                               do. CH.sub.3                                                                           H              H                 --NH.sub.2                                                                             do.                 83 do. do.                                                                               do. OCH.sub.3                                                                          H              H                 --NH.sub.2                                                                             do.                 84 do. do.                                                                               do. H   --OCH.sub.3    H --NH.sub.2      do.                         85 do. do.                                                                               do. H   --NH--C.sub.2 H.sub.4 --K.sub.1                                                               H                 H       do.                 86 do. do.                                                                               do. H   --O--CO--CH.sub.2 --K.sub.1                                                                   H                 H       do.                                   CH.sub.2 --CH--CH.sub.2 --K.sub.1                                               |                                                  87 do. do.                                                                               do. H   --N∠OH   H                 H       do.                                   C.sub.2 H.sub.5                                              88 do. do.                                                                               do. H   --SO.sub.2 --N(CH.sub.3).sub.2                                                                H                 H       do.                 89 do. do.                                                                               do. H   H              --COOC.sub.2 H.sub.4 --K.sub.1                                                                   OH      do.                 90 do. do.                                                                               do. H   H              --COOCH.sub.3     OH      do.                 91 do. H  H   H   H              H                 OH      do.                 92 do. H  H   H   H              --CO--CH.sub.3    OH      do.                 93 do. H  H   H   H              --CO--NH----CO--C.sub.2 H.sub.4 --K.sub.1                                      .                 OH      do.                 94 do. H  H   H   H              --CO--NH--C.sub.6 H.sub.5                                                                        OH      do.                 95 do. H  H   H   OH             H                 H       do.                 96 do. H  H   H   OH             --CO--C.sub.2 H.sub.4 --K.sub.1                                                                  H       do.                                   CH.sub.3                                                                       |                                                   97 do. H  H   H   --SO.sub.2 --NH--CH--C.sub.3 H.sub.6 --K.sub.1                                                H                 OH      do.                 98 do. H  H   H   --NH--C.sub.2 H.sub.4 --OH                                                                    H                 H       do.                 99 do. H  H   H   H              --CO--NH--C.sub.2 H.sub.4 --K.sub.1                                                              OH      do.                 100                                                                               do. H  H   H   H              --O--CO--NH--CH.sub.2 --CH--CH.sub.2                                           --K.sub.1         OH      do.                                                  |                                                                     OH                                            101                                                                               do. H  H   H   --N(CH.sub.3).sub.2                                                                           H                 H       do.                 102                                                                               do. H  H   H   do.            H                 --NH.sub.2                                                                             do.                 103                                                                               do. H  H   H   do.            H                 --NH--C.sub.2 H.sub.4                                                          --OH    do.                 104                                                                               do. H  H   H   do.            H                 --NH--CH.sub.3                                                                         do.                 105                                                                               do. H  H   H   do.            H                 --NH--C.sub.6 H.sub.5                                                                  do.                 106                                                                               do. H  H   H   Br             H                 --NH.sub.2                                                                             do.                 107                                                                               do. H  H   H   Cl             H                 --NH.sub.2                                                                             do.                 108                                                                               do. H  H   H   CH.sub.3       H                 --NH.sub.2                                                                             do.                 109                                                                               do. H  H   CH.sub.3                                                                           H              H                 --NH.sub.2                                                                             do.                 110                                                                               do. H  H   OCH.sub.3                                                                          H              H                 --NH.sub.2                                                                             do.                 111                                                                               do. H  H   H   --OCH.sub.3    H                 --NH.sub.2                                                                             do.                 112                                                                               do. H  H   H   --NH--C.sub.2 H.sub.4 --K.sub.1                                                               H                 H       do.                 113                                                                               do. H  H   H   --O--CO--CH.sub.2 --K.sub.1                                                                   H                 H       do.                                   CH.sub.2 --CH--CH.sub.2 --K.sub.1                                              |     H                 H       do.                 114                                                                               do. H  H   H   --N∠OH                                                                   C.sub.2 H.sub.5                                              115                                                                               do. H  H   H   --SO.sub.2 --N(CH.sub.3).sub.2                                                                H                 H       do.                 116                                                                               do. H  H   H   H              --COO--C.sub.2 H.sub.4 --K.sub.1                                                                 OH      do.                 117                                                                               do. H  H   H   H              --COOCH.sub.3     OH      do.                 118                                                                               do. H  OC.sub.2 H.sub.5                                                                   H   H              H                 OH      do.                 119                                                                               do. H  do. H   H              --CO--CH.sub.3    OH      do.                 120                                                                               do. H  do. H   H              --CO--NH----CO--C.sub.2 H.sub.4 --K.sub.1                                                        OH      do.                 121                                                                               do. H  do. H   H              --CO--NH--C.sub.6 H.sub.5                                                                        OH      do.                 122                                                                               do. H  do. H   OH             H                 H       do.                 123                                                                               do. H  do. H   OH             --CO--C.sub.2 H.sub.4 --K.sub.1                                                                  H       do.                                   CH.sub.3                                                                       |                                                   124                                                                               do. H  do. H   --SO.sub.2 --NH--CH--C.sub.3 H.sub.6 --K.sub.1                                                H                 OH      do.                 125                                                                               do. H  do. H   --NH--C.sub.2 H.sub.4 --OH                                                                    H                 H       do.                 126                                                                               do. H  do. H   H              --CO--NH--C.sub.2 H.sub.4 --K.sub.1                                                              OH      do.                                                  OH                                                                             |                                    127                                                                               do. H  do. H   H              --CO--NH--CH.sub.2 --CH--CH.sub.2                                              --K.sub.1         OH      do.                 128                                                                               do. H  do. H   --N(CH.sub.3).sub.2                                                                           H                 H       do.                 129                                                                               do. H  do. H   do.            H                 --NH.sub.2                                                                             do.                 130                                                                               do. H  do. H   do.            H                 --NH--C.sub.2 H.sub.4                                                          --OH    do.                 131                                                                               do. H  do. H   do.            H                 --NH--CH.sub.3                                                                         do.                 132                                                                               do. H  do. H   do.            H                 --NH--C.sub.6 H.sub.5                                                                  do.                 133                                                                               do. H  do. H   Br             H                 --NH.sub.2                                                                             do.                 134                                                                               do. H  do. H   Cl             H                 --NH.sub.2                                                                             do.                 135                                                                               do. H  do. H   CH.sub.3       H                 --NH.sub.2                                                                             do.                 136                                                                               do. H  do. CH.sub.3                                                                           H              H                 -- NH.sub.2                                                                            do.                 137                                                                               do. H  do. OCH.sub.3                                                                          H              H                 --NH.sub.2                                                                             do.                 138                                                                               do. H  do. H   --OCH.sub.3    H                 --NH.sub.2                                                                             do.                 139                                                                               do. H  do. H   --NH--C.sub.2 H.sub.4 --K.sub.1                                                               H                 H       do.                 140                                                                               do. H  do. H   --O--CO--CH.sub.2 --K.sub.1                                                                   H                 H       do.                                   CH.sub.2 --CH--CH.sub.2 --K.sub.1                                              |                                                   141                                                                               do. H  do. H   --N∠OH   H                 H       do.                                   C.sub.2 H.sub.5                                              142                                                                               do. H  do. H   --SO.sub.2 --N(CH.sub.3).sub.2                                                                H                 H       do.                 143                                                                               do. H  do. H   H              --COO--C.sub.2 H.sub.4 --K.sub.1                                                                 OH      do.                 144                                                                               do. H  do. H   H              --COOCH.sub.3     OH      do.                 __________________________________________________________________________

Table II gives the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##SPC3##

where B₁ to B₆ have the meanings given them in Table II. The anion A⁻ may be any one of those named in the description of the process. The Symbol K may represent any one of the radicals K₁ to K₂₇ listed in Table A; these groupings may be exchanged in any given dye for another of the stated groupings.

                                      Table II                                     __________________________________________________________________________                                                      Shade of                      Ex. B.sub.1                                                                           B.sub.2                                                                            B.sub.3                                                                          B.sub.4       B.sub.5           B.sub.6                                                                            dyeing on                     No.                                              Paper                         __________________________________________________________________________     145 H  CH.sub.3                                                                           H H             --CO--NH----CO--C.sub.2 H.sub.4 --K.sub.1                                                        OH  red                           146 H  CH.sub.3                                                                           H OH            --CO--C.sub.2 H.sub.4 --K.sub.1                                                                  H   do.                                        CH.sub.3                                                                       |                                                        147 H  CH.sub.3                                                                           H --SO.sub.2 --NH--CH--C.sub.3 H.sub.6 --K.sub.1                                               H                 OH  do.                           148 H  CH.sub.3                                                                           H H             --CO--NH--C.sub.2 H.sub.4 --K.sub.1                                                              OH  do.                                                      OH                                                                             |                                          149 H  CH.sub.3                                                                           H H             --CO--NH--CH.sub.2 --CH--CH.sub.2 --K.sub.1                                                      OH  do.                           150 H  CH.sub.3                                                                           H NH--C.sub.2 H.sub.4 --K.sub.1                                                                H                 H   do.                           151 H  CH.sub.3                                                                           H --O--CO--CH.sub.2 --K.sub.1                                                                  H                 H   do.                                        OH                                                                             |                                                                     CH.sub.2 --CH--CH.sub.2 --K.sub.1                                 152 H  CH.sub.3                                                                           H --N∠    H                 H   do.                                        C.sub.2 H.sub.5                                                   153 H  CH.sub.3                                                                           H H             --COOC.sub.2 H.sub.4 --K.sub.1                                                                   OH  do.                           154 CH.sub.3                                                                          CH.sub.3                                                                           H H             --CO--NH----CO--C.sub.2 H.sub.4 --K.sub.1                                                        OH  do.                           155 CH.sub.3                                                                          CH.sub.3                                                                           H OH            --CO--C.sub.2 H.sub.4 --K.sub.1                                                                  H   do.                                        OH.sub.3                                                                       |                                                        156 CH.sub.3                                                                          CH.sub.3                                                                           H --SO.sub.2 --NH--CH--C.sub.3 H.sub.6 --K.sub.1                                               H                 OH  do.                           157 CH.sub.3                                                                          CH.sub.3                                                                           H H             --CO--NH--C.sub.2 H.sub.4 --K.sub.1                                                              OH  do.                                                      OH                                                                             |                                          158 CH.sub.3                                                                          CH.sub.3                                                                           H H             --CO--NH--CH.sub.2 --CH--CH.sub.2 --K.sub.1                                                      OH  do.                           159 CH.sub.3                                                                          CH.sub.3                                                                           H --NH--C.sub.2 H.sub. 4 --K.sub.1                                                             H                 H   do.                           160 CH.sub.3                                                                          CH.sub.3                                                                           H --O--CO--CH.sub.2 --K.sub.1                                                                  H                 H   do.                                        OH                                                                             |                                                                     CH.sub.2 --CH--CH.sub.2 --K.sub.1                                 161 CH.sub.3                                                                          CH.sub.3                                                                           H --N∠    H                 H   do.                                        C.sub.2 H.sub.5                                                   162 CH.sub.3                                                                          CH.sub.3                                                                           H H             --COOC.sub.2 H.sub.4 --K.sub.1                                                                   OH  do.                           163 H  H   H H             --CO--NH----CO--C.sub.2 H.sub.4 --K.sub.1                                                        OH  do.                           164 H  OC.sub.2 H.sub.5                                                                   H H             do.               OH  do.                           165 H  H   H OH            --CO--C.sub.2 H.sub.4 --K.sub.1                                                                  H   do.                           166 H  OC.sub.2 H.sub.5                                                                   H OH            do.               H   do.                                        OH.sub.3                                                                       |                                                        167 H  H   H --SO.sub.2 --NH--CH--C.sub.3 H.sub.6 --K.sub.1                                               H                 OH  do.                           168 H  OC.sub.2 H.sub.5                                                                   H do.           H                 OH  do.                           169 H  H   H H             --CO--NH-- C.sub.2 H.sub.4 --K.sub.1                                                             OH  do.                           170 H  OC.sub.2 H.sub.5                                                                   H H             do.               OH  do.                                                      OH                                                                             |                                          171 H  H   H H             --CO--NH--CH.sub.2 --CH--CH.sub.2 --K.sub.1                                                      OH  do.                           172 H  OC.sub.2 H.sub.5                                                                   H H             do.               OH  do.                           173 H  H   H --NH--C.sub.2 H.sub.4 --K.sub.1                                                              H                 H   do.                           174 H  OC.sub.2 H.sub.5                                                                   H do.           H                 H   do.                           175 H  H   H --O--CO--CH.sub.2 --K.sub.1                                                                  H                 H   do.                           176 H  OC.sub.2 H.sub.5                                                                   H do.           H                 H   do.                                        OH                                                                             |                                                                     CH.sub.2 --CH--CH.sub.2 --K.sub.1                                 177 H  H   H --N∠    H                 H   do.                                        C.sub.2 H.sub.5                                                   178 H  OC.sub.2 H.sub.5                                                                   H do.           H                 H   do.                           __________________________________________________________________________

Table III lists the structural composition of further dyes which may be produced and/or dyed in accordance with the present process. These dyes are of the formula ##EQU36## where B₁, B₂, B₇, B₈ and B₉ have the meanings them in Table III. The anion A⁻ may be any one of those named in the specification, K⁺ may be any one of the radicals K₁ to K₂₇ listed in Table A; these groupings may be exchanged in any given dye for another of the stated groupings. The grouping --CH₂ --K ⁺ may occur once or twice or preferably one and a half times in the dehydrotoluidine radical given inside the square brackets; this grouping is preferably in the 7 and/or 2' position.

                                      Table III                                    __________________________________________________________________________                                           Shade of                                 Ex.                                                                               K   B.sub.1                                                                           B.sub.2                                                                            B.sub.7                                                                            B.sub.8        B.sub.9                                                                             dyeing on                                No.                                   Paper                                    __________________________________________________________________________     179                                                                               K.sub.1 -K.sub.27                                                                  H  CH.sub.3                                                                           OH                 CH.sub.3                                                                            orange                                   180                                                                               do. H  CH.sub.3                                                                           NH.sub.2           H    do.                                      181                                                                               do. H  CH.sub.3                                                                           NH.sub.2           CH.sub.3                                                                            do.                                      182                                                                               do. H  CH.sub.3                                                                           OH  --CH.sub.2 --CH.sub.2 --K.sub.1                                                                    do.                                      183                                                                               do. H  CH.sub.3                                                                           OH  H              CH.sub.3                                                                            do.                                      184                                                                               do. H  CH.sub.3                                                                           OH                 CH.sub.3                                                                            do.                                                        |                                                                     NH--CO--C.sub.2 H.sub.4 --K.sub.1                            185                                                                               do. H  CH.sub.3                                                                           OH  --OCH.sub.3    CH.sub.3                                                                            do.                                      186                                                                               do. H  CH.sub.3                                                                           OH  --CH.sub.2 --K.sub.1                                                                          CH.sub.3                                                                            do.                                      187                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           OH                 CH.sub.3                                                                            do.                                      188                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           NH.sub.2           H    do.                                      189                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           NH.sub.2           CH.sub.3                                                                            do.                                      190                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           OH  --CH.sub.2 --CH.sub.2 --K.sub.1                                                                    do.                                      191                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           OH  H              CH.sub.3                                                                            do.                                      192                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           OH                 CH.sub.3                                                                            do.                                                        |                                                                     NH--CO--C.sub.2 H.sub.4 --K.sub.1                            193                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           OH  --OCH.sub.3    CH.sub.3                                                                            do.                                      194                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           OH  --CH.sub.2 --K.sub.1                                                                          CH.sub.3                                                                            do.                                      195                                                                               do. H  H   OH                 CH.sub.3                                                                            do.                                      196                                                                               do. H  H   NH.sub.2           H    do.                                      197                                                                               do. H  H   NH.sub.2           CH.sub.3                                                                            do.                                      198                                                                               do. H  H   OH  --CH.sub.2 --CH.sub.2 --K.sub.1                                                                    do.                                      199                                                                               do. H  H   OH  H              CH.sub.3                                                                            do.                                      200                                                                               do. H  H   OH                 CH.sub.3                                                                            do.                                                        |                                                                     NH--CO--C.sub.2 H.sub.4 --K.sub.1                            201                                                                               do. H  H   OH  --OCH.sub.3    CH.sub.3                                                                            do.                                      202                                                                               do. H  H   OH  --CH.sub.2 --K.sub.1                                                                          CH.sub.3                                                                            do.                                      203                                                                               do. H  OC.sub.2 H.sub.5                                                                   OH                 CH.sub.3                                                                            do.                                      204                                                                               do. H  OC.sub.2 H.sub.5                                                                   NH.sub.2           H    do.                                      205                                                                               do. H  OC.sub.2 H.sub.5                                                                   NH.sub.2           CH.sub.3                                                                            do.                                      206                                                                               do. H  OC.sub.2 H.sub.5                                                                   OH  --CH.sub.2 --CH.sub.2 --K.sub.1                                                                    do.                                      207                                                                               do. H  OC.sub.2 H.sub.5                                                                   OH  H              CH.sub.3                                                                            do.                                      208                                                                               do. H  OC.sub.2 H.sub.5                                                                   OH                 CH.sub.3                                                                            do.                                                        |                                                                     NH--CO--C.sub.2 H.sub.4 --K.sub.1                            209                                                                               do. H  OC.sub.2 H.sub.5                                                                   OH  --OCH.sub.3    CH.sub.3                                                                            do.                                      210                                                                               do. H  OC.sub.2 H.sub.5                                                                   OH   --CH.sub.2 --K.sub.1                                                                         CH.sub.3                                                                            do.                                      __________________________________________________________________________

Table IV sets forth the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##EQU37## where B₁, B₂ and B₇, B₈ and B₉ have the meanings given them in Table IV.

The anion A⁻ may be any one of those named in the specification. K may stand for any of the radicals K₁ to K₂₇ listed in Table A. These groupings may be exchanged in any given dye for another of the stated groupings.

                                      Table IV                                     __________________________________________________________________________     Ex.                               Shade of                                     No.                                                                               B.sub.1                                                                           B.sub.2                                                                            B.sub.7                                                                           B.sub.8          B.sub.9                                                                            dyeing on                                                                      Paper                                        __________________________________________________________________________     211                                                                               H  CH.sub.3                                                                           OH --CH.sub.2 --CH.sub.2 --K.sub.1                                                                     orange                                       212                                                                               CH.sub.3                                                                          CH.sub.3                                                                           OH do.              do. do.                                          213                                                                               H  H   OH do.              do. do.                                          214                                                                               H  OC.sub.2 H.sub.5                                                                   OH do.              do. do.                                          215                                                                               H  CH.sub.3                                                                           OH                  CH.sub.3                                                                           do.                                                       |                                                                     NH--CO--C.sub.2 H.sub.4 --K.sub.1                                 216                                                                               CH.sub.3                                                                          CH.sub.3                                                                           OH do.              do. do.                                          217                                                                               H  H   OH do.              do. do.                                          218                                                                               H  OC.sub.2 H.sub.5                                                                   OH do.              do. do.                                          219                                                                               H  CH.sub.3                                                                           OH --CH.sub.2 --K.sub.1                                                                            CH.sub.3                                                                           do.                                          220                                                                               CH.sub.3                                                                          CH.sub.3                                                                           OH do.              do. do.                                          221                                                                               H  H   OH do.              do. do.                                          222                                                                               H  OC.sub.2 H.sub.5                                                                   OH do.              do. do.                                          __________________________________________________________________________

Table V shows the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##EQU38## where B₁, B₂ and X have the meanings given them in Table. The anion A⁻ may be any one of those named in the specification. K⁺ may stand for any of the radicals K₁ to K₂₇ listed in Table A. These groupings may be exchanged in any given dye for another of the stated groupings. The grouping --CH₂ --K⁺ may occur once or twice or preferably one and a half times in the dehydrotoluidine radical given in square brackets; this grouping occupies preferably the 7 and/or 2' position.

                  Table V                                                          ______________________________________                                                                   X = radical of                                                                              Shade of                                Ex.  K       B.sub.1                                                                               B.sub.2                                                                              coupling compo-                                                                             dyeing on                               No.                       nent         paper                                   ______________________________________                                         223  K.sub.1 -K.sub.27                                                                      H      CH.sub.3                                                                             --OH         yellow                                  224  do.     H      H     do.          do.                                     225  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     226  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                     227  do.     H      CH.sub.3                                                                             HO----CH.sub.3                                                                              do.                                     228  do.     H      H     do.          do.                                     229  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     230  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                     231  do.     H      CH.sub.3                                                                             HO--         do.                                                               |                                                                     CH.sub.3                                             232  do.     H      H     do.          do.                                     233  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     234  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                                               CH.sub.3                                                                       |                                           235  do.     H      CH.sub.3                                                                             HO--         do.                                     236  do.     H      H     do.          do.                                     237  do.     CH.sub.3                                                                              CH.sub. 3                                                                            do.          do.                                     238  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                                               CH                                                                             |                                           239  do.     H      CH.sub.3                                                                             HO--         orange                                  240  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     241  do.     H      H     do.          do.                                     242  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                                               CH                                                                             |                                           243  do.     H      H     HO--         do.                                     244  do.     H      H     do.          do.                                     245  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     246  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                                               OH                                                                             |                                           247  do.     H      CH.sub.3                                                                             HO----CH.sub.2 OH                                                                           do.                                                               |                                           248  do.     H      H     do.          do.                                     249  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     OH                                                                             |                                                                     250  do.     H      OC.sub.2 H.sub.5                                                                     HO----CH.sub.2 OH                                                                           do.                                                               OH                                                                             |                                           251  do.     H      CH.sub.3                                                                             HO----Cl     do.                                     252  do.     H      H     do.          do.                                     253  do.     CH.sub. 3                                                                             CH.sub.3                                                                             do.          do.                                     254  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                     255  do.     H      CH.sub.3                                                                             H.sub.2 N--  do.                                     256  do.     H      H     do.          do.                                     257  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     258  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                                               OH                                                                             |                                           259  do.     H      CH.sub.3                                                                             H.sub.2 N--  do.                                     260  do.     H      H     do.          do.                                     261  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     262  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                                               CH.sub.3                                             263  do.     H      H     |-                                                                    H.sub.2 N--  yellow                                  264  do.     H      H     do.          do.                                     265  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     266  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                                               CH.sub.3                                                                       |                                           267  do.     H      CH.sub.3                                                                             H.sub.2 N--  do.                                                               |                                                                     OCH.sub.3                                            268  do.     H      H     do.          do.                                     269  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     270  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                                                            NH.sub.2                                                          51                                                   271  do.     H      CH.sub.3                                                                             H.sub.2 N--  red.                                    272  do.     H      H     do.          do.                                     273  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     274  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                                               NH.sub.2                                                                       |                                           275  do.     H      CH.sub.3                                                                             H.sub.2 N----C1                                                                             do.                                     276  do.     H      H     do.          do.                                     277  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     278  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                                               NH.sub.2                                                                       |                                           279  do.     H      CH.sub.3                                                                             H.sub.2 N----CH.sub.3                                                                       do.                                     280  do.     H      H     do.          do.                                     281  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     282  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                                               CH.sub.3                                                                       |                                           283  do.     H      CH.sub.3                                                                             H.sub.2 N--  yellow                                  284  do.     H      H     do.          do.                                     285  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                     286  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     287  do.     H      CH.sub.3           red-orange                                                        |                                                                     OH                                                   288  do.     H      H     do.          do.                                     289  do.     CH.sub.3                                                                              CH.sub.3                                                                             do.          do.                                     290  do.     H      OC.sub.2 H.sub.5                                                                     do.          do.                                     ______________________________________                                    

Table VI sets forth the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##EQU39## where B₁, B₂, B₁₁, B₁₂, B₁₃, B₁₄ and B₁₅ have the meanings given them in Table VI.

The anion A⁻ may be any one of those named in the specification. K⁺ may stand for any one of the radicals K₁ to K₂₇ listed in Table A. These groupings may be exchanged in any given dye for one of the other stated groupings. The grouping --CH₂ --K⁺ may occur once or twice or preferably one and a half times in the dehydrotoluidine radical shown in square brackets; this grouping stands preferably in the 7 and/or 2' position.

                                      Table VI                                     __________________________________________________________________________     Exam-                                                                              K    B.sub.1                                                                            B.sub.2                                                                             B.sub.11                                                                            B.sub.12 B.sub.13                                                                           B.sub.14                                                                             B.sub.15                                                                           Shade of                         ple                                           dyeing on                        No.                                           Paper                            __________________________________________________________________________     291 K.sub.1                                                                             H   CH.sub.3                                                                            OCH.sub.3                                                                           H        H   --CH.sub.2 --K.sub.1                                                                 H   yellow                           292-                                                                               K.sub.2 -K.sub.27                                                                   H   CH.sub.3                                                                            do.  H        H   --CH.sub.2 --K.sub.1                                                                 H   do.                              318                                                                            319 K.sub.1 -K.sub.27                                                                   H   CH.sub.3                                                                            H    H        H   H     H   do.                              320 do.  H   do.  OCH.sub.3                                                                           H        H   OCH.sub.3                                                                            H   do.                              321 do.  H   do.  do.  H        Cl  OCH.sub.3                                                                            H   do.                              322 do.  H   do.  H    H        Cl  H     H   do.                              323 do.  H   do.  OCH.sub.3                                                                           --CH.sub.2 --K.sub.1                                                                    H   --CH.sub.2 --K.sub.1                                                                 H   do.                              324 do.  H   do.  H    --NH--CO--CH.sub.2 --K.sub.1                                                            H   H     H   do.                              325 do.  H   do.  CH.sub.3                                                                            H        H   H     H   do.                              326 do.  H   do.  CH.sub.3                                                                            H        H   --CH.sub.2 --K.sub.1                                                                 H   do.                              327 do.  H   H    OCH.sub.3                                                                           H        H   --CH.sub.2 --K.sub.1                                                                 H   do.                              328 do.  H   H    H    H        H   H     H   do.                              329 do.  H   H    OCH.sub.3                                                                           H        H   OCH.sub.3                                                                            H   do.                              330 do.  H   H    OCH.sub.3                                                                           H        Cl  do.   H   do.                              331 do.  H   H    H    H        Cl  H     H   do.                              332 do.  H   H    OCH.sub.3                                                                           --CH.sub.2 --K.sub.1                                                                    H   --CH.sub.2 --K.sub.1                                                                 H   do.                              333 do.  H   H    H    --NH--CO--CH.sub.2 --K.sub.1                                                            H   H     H   do.                              334 do.  H   H    CH.sub.3                                                                            H        H   H     H   do.                              335 do.  H   H    CH.sub.3                                                                            H        H   --CH.sub.2 --K.sub.1                                                                 H   do.                              336 do.  CH.sub.3                                                                           CH.sub.3                                                                            CH.sub.3                                                                            H        H   do.   H   do.                              337 do.  do. do.  do.  H        H   do.   H   do.                              338 do.  do. do.  H    H        H   H     H   do.                              339 do.  do. do.  OCH.sub.3                                                                           H        H   OCH.sub.3                                                                            H   do.                              340 do.  do. do.  do.  H        Cl  do.   H   do.                              341 do.  do. do.  H    H        Cl  H     H   do.                              342 do.  do. do.  OCH.sub.3                                                                           --CH.sub.2 --K.sub.1                                                                    H   --CH.sub.2 --K.sub.1                                                                 H   do.                              343 do.  do. do.  H    --NH--CO--CH.sub.2 --K.sub.1                                                            H   H     H   do.                              344 do.  do. do.  CH.sub.3                                                                            H        H   H     H   do.                              345 do.  do. do.  do.  H        H   --CH.sub.2 --K.sub.1                                                                 H   do.                              346 do.  H   O.sub.2 CH.sub.5                                                                    CH.sub.3                                                                            H        H   CH.sub.2 --K.sub.1                                                                   H   do.                              347 do.  H   do.  do.  H        H   do.   H   do.                              348 do.  H   do.  H    H        H   H     H   do.                              349 do.  H   do.  OCH.sub.3                                                                           H        H   OCH.sub.3                                                                            H   do.                              350 do.  H   do.  do.  H        Cl  do.   H   do.                              351 do.  H   do.  H    H        Cl  H     H   do.                              352 do.  H   do.  OCH.sub.3                                                                           CH.sub.2 --K.sub.1                                                                      H   CH.sub.2 --K.sub.1                                                                   H   do.                              353 do.  H   do.  H    --NH--CO--CH.sub.2 --K.sub.1                                                            H   H     H   do.                              354 do.  H   do.  CH.sub.3                                                                            H        H   H     H   do.                              355 do.  H   do.  do.  H        H   CH.sub.2 --K.sub.1                                                                   H   do.                              __________________________________________________________________________

Table VII gives the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##EQU40## where B₁, B₂, B₁₁, B₁₂, B₁₃, B₁₄ and B₁₅ have the meanings assigned to them in Table VII. The anion A⁻ may be any one of those named in the specification. For the symbol K the notes on Table I and II apply.

                                      Table VII                                    __________________________________________________________________________     Exam-                                                                              B.sub.1                                                                            B.sub.2                                                                             B.sub.11                                                                           B.sub.12 B.sub.13                                                                           B.sub.14                                                                             B.sub.15                                                                           Shade of                                ple                                    dyeing on                               No.                                     Paper                                 __________________________________________________________________________     356 H   CH.sub.3                                                                            CH.sub.3                                                                           CH.sub.2 --K.sub.1                                                                      CH.sub.3                                                                           CH.sub.2 --K.sub.1                                                                   CH.sub.3                                                                           yellow                                 357 H   do.  do. CH.sub.2 --K.sub.2                                                                      do. CH.sub.2 --K.sub.2                                                                   do. do.                                    358 H   do.  do. CH.sub.2 --K.sub.3                                                                      do. CH.sub.2 --K.sub.3                                                                   do. do.                                    359 H   do.  do. CH.sub.2 --K.sub.10                                                                     do. CH.sub.2 --K.sub.10                                                                  do. do.                                    360 H   do.  do. CH.sub.2 --K.sub.12                                                                     do. CH.sub.2 --K.sub.12                                                                  do. do.                                    361 H   do.  do. CH.sub.2 --K.sub.19                                                                     do. CH.sub.2 --K.sub.19                                                                  do. do.                                    362 H   do.  do. CH.sub.2 --K.sub.22                                                                     do. CH.sub.2 --K.sub.22                                                                  do. do.                                    363 H   H    do. --CH.sub.2 --K.sub.1                                                                    do. CH.sub.2 --K.sub.1                                                                   do. do.                                    364 CH.sub.3                                                                           CH.sub.3                                                                            do. do.      do. do.   do. do.                                    365 H   OC.sub.2 H.sub.5                                                                    do. do.      do. do.   do. do.                                    366 H   CH.sub.3                                                                            OCH.sub.3                                                                          CH.sub.2 --K.sub.1                                                                      H   CH.sub.2 --K.sub.1                                                                   H   do.                                    367 H   H    do. do.      H   do.   H   do.                                    368 CH.sub.3                                                                           CH.sub.3                                                                            do. do.      H   do.   H   do.                                    369 H   OC.sub.2 H.sub.5                                                                    do. do.      H   do.   H   do.                                    370 H   CH.sub.3                                                                            H   --NH--CO--CH.sub.2 --K.sub.1                                                            H   H     H   do.                                    371 H   H    H   do.      H   H     H   do.                                    372 CH.sub.3                                                                           CH.sub.3                                                                            H   do.      H   H     H   do.                                    373 H   OC.sub.2 H.sub.5                                                                    H   do.      H   H     H   do.                                    374 H   CH.sub.3                                                                            CH.sub.3                                                                           H        H   --CH.sub.2 --K.sub.1                                                                 H   do.                                    375 H   H    do. H        H   do.   H   do.                                    376 CH.sub.3                                                                           CH.sub.3                                                                            do. H        H   do.   H   do.                                    377 H   OC.sub.2 H.sub.5                                                                    do. H        H   do.   H   do.                                    __________________________________________________________________________

Table VIII gives the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##EQU41## where B₁ B₂ and B₁₆ have the meanings given them in Table VIII. The anion A⁻ may be any one of those named in the specification. For the symbol K⁺ the notes on Table I apply. The grouping --CH₂ --K⁺ may occur once or twice or preferably one and a half times in the dehydrotoluidine radical shown in square brackets; this grouping occupies preferably the 7 and/or 2' position.

                                      Table VIII                                   __________________________________________________________________________     Example                                                                             K    B.sub.1                                                                            B.sub.2                                                                             B.sub.16   Shade of                                          No.                          dyeing on                                                                       Paper                                           __________________________________________________________________________     378  K.sub.1 -K.sub.27                                                                   H   CH.sub.3                                                                            --OCH.sub.3                                                                               yellow                                           379  do.  H   CH.sub.3                                                                            --OC.sub.4 H.sub.9                                                                        do.                                              380  do.  H   do.  --NH--CH.sub.3                                                                            do.                                              381  do.  H   do.  --NH--C.sub.4 H.sub.9                                                                     do.                                              382  do.  H   CH.sub.3                                                                            --NH--C.sub.2 H.sub.4 --K.sub.1                                                           do.                                              383  do.  H   do.  --NH.sub.2 do.                                              384  do.  H   do.  --O--C.sub.2 H.sub.4 --K.sub.1                                                            do.                                              385  do.  H   CH.sub.3                                                                            --O--      do.                                              386  do.  H   CH.sub.3                                                                            --O----CH.sub.3                                                                           do.                                              387  do.  H   CH.sub.3                                                                            --O----OCH.sub.3                                                                          do.                                                                 |                                                                     CH.sub.3                                                    388  do.  H   CH.sub.3                                                                            --O----OCH.sub.3                                                                          do.                                                                 |                                                                     CH.sub.2 --K.sub.1                                          389  do.  H   H    --OCH.sub.3                                                                               do.                                              390  do.  CH.sub.3                                                                           CH.sub.3                                                                            do.        do.                                              391  do.  H   OC.sub.2 H.sub.5                                                                    do.        do.                                              392  do.  H   H    OC.sub.4 H.sub.9                                                                          do.                                              393  do.  CH.sub.3                                                                           CH.sub.3                                                                            do.        do.                                              394  do.  H   OC.sub.2 H.sub.5                                                                    do.        do.                                              395  do.  H   H    --NH--CH.sub.3                                                                            do.                                              396  do.  CH.sub.3                                                                           CH.sub.3                                                                            do.        do.                                              397  do.  H   OC.sub.2 H.sub.5                                                                    do.        do.                                              398  do.  H   H    --NH--C.sub.4 H.sub.9                                                                     do.                                              399  do.  CH.sub.3                                                                           CH.sub.3                                                                            do.        do.                                              400  do.  H   OC.sub.2 H.sub.5                                                                    do.        do.                                              401  do.  H   H    --NH--C.sub.2 H.sub.4 --K.sub.1                                                           do.                                              402  do.  CH.sub.3                                                                           CH.sub.3                                                                            do.        do.                                              403  K.sub.1 -K.sub.27                                                                   H   OC.sub.2 H.sub.5                                                                    --NH--C.sub.2 H.sub.4 --K.sub.1                                                           yellow                                           404  do.  H   H    --NH.sub.2 do.                                              405  do.  CH.sub.3                                                                           CH.sub.3                                                                            do.        do.                                              406  do.  H   OC.sub.2 H.sub.5                                                                    do.        do.                                              407  do.  H   H    --O--C.sub.2 H.sub.4 --K.sub.1                                                            do.                                              408  do.  CH.sub.3                                                                           CH.sub.3                                                                            do.        do.                                              409  do.  H   OC.sub.2 H.sub.5                                                                    do.        do.                                              410  do.  H   H    --O--      do.                                              411  do.  CH.sub.3                                                                           CH.sub.3                                                                            do.        do.                                              412  do.  H   OC.sub.2 H.sub.5                                                                    do.        do.                                              413  do.  H   H    --O----CH.sub.3                                                                           do.                                              414  do.  CH.sub.3                                                                           CH.sub.3                                                                            do.        do.                                              415  do.  H   OC.sub.2 H.sub.5                                                                    do.        do.                                              416  do.  H   H    --O----OCH.sub.3                                                                          do.                                                                 |                                                                     CH.sub.3                                                    417  do.  CH.sub.3                                                                           CH.sub.3                                                                            do.        do.                                              418  do.  H   OC.sub.2 H.sub.5                                                                    do.        do.                                              419  do.  H   H    --O----OCH do.                                                                 |-   CH.sub.2 --K.sub.1                            420  do.  CH.sub.3                                                                           CH.sub.3                                                                            do.        do.                                              421  do.  H   OC.sub.2 H.sub.5                                                                    do.        do.                                              __________________________________________________________________________

Table IX lists the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##EQU42## where B₁, B₂ and B₁₆ have the meanings given them in Table IX. The anion A⁻ may be any one of those named in the specification.

                  Table IX                                                         ______________________________________                                         Example                                                                               B.sub.1 B.sub.2  B.sub.16     Shade                                     No.                                  of dyeing                                                                      on Paper                                  ______________________________________                                         422    H       CH.sub.3 --NH--C.sub.2 H.sub.4 --K.sub.1                                                             yellow                                    423    H       CH.sub.3 --O--C.sub.2 H.sub.4 --K.sub.1                                                              do.                                       424    H       CH.sub.3 --O----OCH.sub.3                                                                            do.                                                               |                                                                     CH.sub.2 --K.sub.1                                     425    H       H        --NH--C.sub.2 H.sub.4 --K.sub.1                                                             do.                                       426    CH.sub.3                                                                               CH.sub.3 do.          do.                                       427    H       OC.sub.2 H.sub.5                                                                        do.          do.                                       428    H       H        --O--C.sub.2 H.sub.4 --K.sub.1                                                              do.                                       429    CH.sub.3                                                                               CH.sub.3 do.          do.                                       430    H       OC.sub.2 H.sub.5                                                                        do.          do.                                       431    H       H        --O----O--CH.sub.3                                                                          do.                                                               |                                                                     CH.sub.2 --K.sub.1                                     432    CH.sub.3                                                                               CH.sub.3 do.          do.                                       433    H       OC.sub.2 H.sub.5                                                                        do.          do.                                       ______________________________________                                    

Table X sets forth the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##SPC4##

where B₁, B₂ and B₂₀ to B₂₃ have the meanings given them in Table X. F may be any one of the radicals F₁ to F₁₃ listed in Table B. These groupings may be exchanged in any given dye for another of the stated groupings. The grouping --CH₂ --F may occur once or twice or preferably one and a half times in the dehydrotoluidine radical shown in square brackets; this grouping is preferably in the 7 and/or 2' position.

                  Table B                                                          ______________________________________                                         F may stand for F.sub.1 to F.sub.13 which represent the following              groupings                                                                                             CH.sub.3                                                F.sub.1  represent     --N∠                                                                     CH.sub.3                                                F.sub.2  "             --N(C.sub.2 H.sub.5).sub.2                                                     CH.sub.3                                                                       |                                              F.sub.3  represent     --N--C.sub.2 H.sub.5                                                           CH.sub.3                                                                       |                                              F.sub.4  "             --N                                                                            |                                              F.sub.5  "             --NH.sub.2                                              F.sub.6  "             --NH--CH.sub.3                                          F.sub.7  "             --NH--C.sub.3 H.sub.7                                                          CH.sub.2 --CH.sub.2                                     F.sub.8  "             --N∠∠O                                                             CH.sub.2 --CH.sub.2                                                            CH.sub.2 --CH.sub.2                                     F.sub.9  "             --N∠|                                                           CH.sub.2 --CH.sub.2                                                            CH.sub.2 --CH.sub.3                                     F.sub.10 "             --N∠∠CH.sub.2                                                      CH.sub.2 --CH.sub.2                                                            CH.sub.2 --                                             F.sub.11 "             --N∠                                                                     CH.sub.3                                                                       CH.sub.3                                                F.sub.12 "             --N∠                                                                     C.sub.2 H.sub.4 OH                                                             C.sub.2 H.sub.4 --OH                                    F.sub.13 "             --N∠                                                                     C.sub.2 H.sub.4 --OH                                    ______________________________________                                    

                                      TABLE X                                      __________________________________________________________________________     Ex.                                                                               F   B.sub.1                                                                           B.sub.2                                                                            B.sub.20                                                                           B.sub.21      B.sub.22         B.sub.23                                                                               Shade                 No.                                                      of dyeing                                                                      on                    __________________________________________________________________________                                                              Paper                 434                                                                               F.sub.1 -F.sub.13                                                                  H  CH.sub.3                                                                           H   H             H                OH      red                   435                                                                               do. H  CH.sub.3                                                                           H   H             --CO--CH.sub.3   OH      do.                   436                                                                               do. H  CH.sub.3                                                                           H   H             --CO--NH----CO--C.sub.2 H.sub.4 --F.sub.1                                                       OH      do.                   437                                                                               do. H  CH.sub.3                                                                           H   H             --CO--NH--C.sub.6 H.sub.5                                                                       OH      do.                   438                                                                               do. H  CH.sub.3                                                                           H   OH            H                H       do.                   439                                                                               do. H  CH.sub.3                                                                           H   OH            --CO--C.sub.2 H.sub.4 --F.sub.1                                                                 H       do.                                     CH.sub.3                                                                       |                                                   440                                                                               do. H  CH.sub.3                                                                           H   --SO.sub.2 --NH--CH--C.sub.3 H.sub.6 --F.sub.1                                               H                OH      do.                   441                                                                               do. H  CH.sub.3                                                                           H   H             --CO--NH-- C.sub.2 H.sub.4 --F.sub.1                                                            OH      do.                                                   OH                                                                             |                                     442                                                                               do. H  CH.sub.3                                                                           H   H             --CO--NH--CH.sub.2 --CH--CH.sub.2                                              --F.sub.1        OH      do.                   443                                                                               do. H  CH.sub.3                                                                           H   --NH--C.sub.2 H.sub.4 --OH                                                                   H                H       do.                   444                                                                               do. H  CH.sub.3                                                                           H   --N(CH.sub.3).sub.2                                                                          H                H       do.                   445                                                                               do. H  CH.sub.3                                                                           H   do.           H                NH.sub.2                                                                               do.                   446                                                                               do. H  CH.sub.3                                                                           H   do.           H                --NH--C.sub.2 H.sub.4                                                          --OH    do.                   447                                                                               do. H  CH.sub.3                                                                           H   --N(CH.sub.3).sub.2                                                                          H                --NH--CH.sub.3                                                                         do.                   448                                                                               do. H  CH.sub.3                                                                           H   do.           H                --NH--C.sub.6 H.sub.5                                                                  do.                   449                                                                               do. H  CH.sub.3                                                                           H   Br            H                --NH.sub.2                                                                             do.                   450                                                                               do. H  CH.sub.3                                                                           H   Cl            H                --NH.sub.2                                                                             do.                   451                                                                               do. H  CH.sub.3                                                                           H   CH.sub.3      H                 NH.sub.2                                                                              do.                   452                                                                               do. H  CH.sub.3                                                                           CH.sub.3                                                                           H             H                --NH.sub.2                                                                             do.                   453                                                                               do. H  CH.sub.3                                                                           OCH.sub.3                                                                          H             H                --NH.sub.2                                                                             do.                   454                                                                               do. H  CH.sub.3                                                                           H   OCH.sub.3     H                 NH.sub.2                                                                              do.                   455                                                                               do. H  CH.sub.3                                                                           H   --NH--C.sub.2 H.sub.4 --F.sub.1                                                              H                H       do.                   456                                                                               do. H  CH.sub.3                                                                           H   --O--CO--CH.sub.2 --F.sub.1                                                                  H                H       do.                                     CH.sub.2 --CH--CH.sub.2 --F.sub.1                                              |                                                   457                                                                               do. H  CH.sub.3                                                                           H   --N∠OH  H                H       do.                                     C.sub.2 H.sub.5                                              458                                                                               do. H  CH.sub.3                                                                           H   --SO.sub.2 --N(CH.sub.3).sub.2                                                               H                H       do.                   459                                                                               do. H  CH.sub.3                                                                           H   H             --COOC.sub.2 H.sub.4 --F.sub.1                                                                  OH      do.                   460                                                                               do. H  CH.sub.3                                                                           H   H             --COOCH.sub.3    OH      do.                   461                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   H             H                OH      do.                   462                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   H             --CO--CH.sub.3   OH      do.                   463                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   H             --CO--NH----CO--C.sub.2 H.sub.4 --F.sub.1                                                       OH      do.                   464                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   H             -- CO--NH--C.sub.6 H.sub.5                                                                      OH      do.                   465                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   OH            H                H       do.                   466                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   OH            --CO--C.sub.2 H.sub.4 --F.sub.1                                                                 H       do.                                     CH.sub.3                                                                       |                                                   467                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   --SO.sub.2 --NH--CH--C.sub.3 H.sub.6 --F.sub.1                                               H                OH      do.                   468                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   H             --CO--NH--C.sub.2 H.sub.4 --F.sub.1                                                             OH      do.                                                   OH                                                                             |                                     469                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   H             --CO--NH--CH.sub.2 --CH--CH.sub.2                                              --F.sub.1        OH      do.                   470                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   --NH--C.sub.2 H.sub.4 --OH                                                                   H                H       do.                   471                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   --N(CH.sub.3).sub.2                                                                          H                H       do.                   472                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   do.           H                NH.sub.2                                                                               do.                   473                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   do.           H                --NH--C.sub.2 H.sub.4                                                          --OH    do.                   474                                                                               do. CH.sub.3                                                                          CH.sub.3                                                                           H   --N(CH.sub.3).sub.2                                                                          H                --NH--CH.sub.3                                                                         do.                   475                                                                               do. do.                                                                               do. H   do.           H                --NH--C.sub.6 H.sub.5                                                                  do.                   476                                                                               do. do.                                                                               do. H   Br            H                --NH.sub.2                                                                             do.                   477                                                                               do. do.                                                                               do. H   Cl            H                --NH.sub.2                                                                             do.                   478                                                                               do. do.                                                                               do. H   CH.sub.3      H                --NH.sub.2                                                                             do.                   479                                                                               do. do.                                                                               do. CH.sub.3                                                                           H             H                --NH.sub.2                                                                             do.                   480                                                                               do. do.                                                                               do. OCH.sub.3                                                                          H             H                --NH.sub.2                                                                             do.                   481                                                                               do. do.                                                                               do. H   OCH.sub.3     H                --NH.sub.2                                                                             do.                   482                                                                               do. do.                                                                               do. H   --NH--C.sub.2 H.sub.4 --F.sub.1                                                              H                H       do.                   483                                                                               do. do.                                                                               do. H   --O--CO--CH.sub.2 --F.sub.1                                                                  H                H       do.                                     CH.sub.2 --CH--CH.sub.2 --F.sub.1                                              |                                                   484                                                                               do. do.                                                                               do. H   --∠OH   H                H       do.                                     C.sub.2 H.sub.5                                              485                                                                               do. do.                                                                               do. H   --SO.sub.2 --N(CH.sub.3).sub.2                                                               H                H       do.                   486                                                                               do. do.                                                                               do. H   H             --COOC.sub.2 H.sub.4 --F.sub.1                                                                  OH      do.                   487                                                                               do. do.                                                                               do. H   H             --COOCH.sub.3    OH      do.                   488                                                                               do. H  H   H   H             H                OH      do.                   489                                                                               do. H  H   H   H             --CO--CH.sub.3   OH      do.                   490                                                                               do. H  H   H   H             --CO--NH--CO--C.sub.2 H.sub.4 --F.sub.1                                                         OH      do.                   491                                                                               do. H  H   H   H             --CO--NH--C.sub.6 H.sub.5                                                                       OH      do.                   492                                                                               do. H  H   H   OH            H                H       do.                   493                                                                               do. H  H   H   OH            --CO--C.sub.2 H.sub.4 --F.sub.1                                                                 H       do.                                     CH.sub.3                                                                       |                                                   494                                                                               do. H  H   H   --SO.sub.2 --NH--CH--C.sub.3 H.sub.6 --F.sub.1                                               H                OH      do.                   495                                                                               do. H  H   H   H             --CO--NH--C.sub.2 H.sub.4 --F.sub.1                                                             OH      do.                                                   OH                                                                             |                                     496                                                                               do. H  H   H   H             --CO--NH--CH.sub.2 --CH--CH.sub.2                                              --F.sub.1        OH      do.                   497                                                                               do. H  H   H   --NH--C.sub.2 H.sub.4 OH                                                                     H                H       do.                   498                                                                               do. H  H   H   --N(CH.sub.3).sub.2                                                                          H                H       do.                   499                                                                               do. H  H   H   do.           H                --NH--C.sub.2 H.sub.4                                                          --OH    do.                   500                                                                               do. H  H   H   do.           H                --NH--C.sub.2 H.sub.4                                                          --OH    do.                   501                                                                               do. H  H   H   do.           H                --NH--OH.sub.3                                                                         do.                   502                                                                               do. H  H   H   do.           H                --NH--C.sub.6 H.sub.5                                                                  do.                   503                                                                               do. H  H   H   Br            H                --NH--C.sub.6 H.sub.5                                                                  do.                   504                                                                               do. H  H   H   Cl            H                --NH.sub.2                                                                             do.                   505                                                                               do. H  H   H   CH.sub.3      H                --NH.sub.2                                                                             do.                   506                                                                               do. H  H   CH.sub.3                                                                           H             H                --NH.sub.2                                                                             do.                   507                                                                               do. H  H   OCH.sub.3                                                                          H             H                --NH.sub.2                                                                             do.                   508                                                                               do. H  H   H   OCH.sub.3     H                --NH.sub.2                                                                             do.                   509                                                                               do. H  H   H   --NH--C.sub.2 H.sub.4 --F.sub.1                                                              H                H       do.                   510                                                                               do. H  H   H   --O--CO--CH.sub.2 --F.sub.1                                                                  H                H       do.                                     CH.sub.2 --OH--CH.sub. 2 --F.sub.1                                             |                                                   511                                                                               do. H  H   H   --N∠OH  H                H       do.                                     C.sub.2 H.sub.5                                              512                                                                               do. H  H   H   --SO.sub.2 --N(CH.sub.3).sub.2                                                               H                H       do.                   513                                                                               do. H  H   H   H             --COOC.sub.2 H.sub.4 --F.sub.1                                                                  OH      do.                   514                                                                               do. H  H   H   H             --COOCH.sub.3    OH      do.                   515                                                                               do. H  OC.sub.2 H.sub.5                                                                   H   H             H                OH      do.                   516                                                                               do. H  do. H   H             --CO--CH.sub.3   OH      do.                   517                                                                               do. H  do. H   H             --CO--NH----CO--C.sub.2 H.sub.4 --F.sub.1                                                       OH      do.                   518                                                                               do. H  do. H   H             --CO--NH--C.sub.6 H.sub.5                                                                       OH      do.                   519                                                                               do. H  do. H   OH            H                H       do.                   520                                                                               do. H  do. H   OH            --CO--C.sub.2 H.sub.4 --F.sub.1                                                                 H       do.                                     OH                                                                             |                                                   521                                                                               do. H  do. H   --SO.sub.2 --NH--CH--C.sub.3 H.sub.6 --F.sub.1                                               H                OH      do.                   522                                                                               do. H  do. H   H             --CO--NH--C.sub.2 H.sub.4 --F.sub.1                                                             OH      do.                                                   OH                                                                             |                                     523                                                                               do. H  do. H   H             --CO--NH--CH.sub.2 --CH--CH.sub.2                                              --F.sub.1        OH      do.                   524                                                                               do. H  do. H   --NH--C.sub.2 H.sub.4 OH                                                                     H                H       do.                   525                                                                               do. H  do. H   --N(CH.sub.3).sub.2                                                                          H                H       do.                   526                                                                               do. H  do. H   do.           H                NH.sub.2                                                                               do.                   527                                                                               do. H  do. H   do.           H                --NH--C.sub.2 H.sub.4                                                          --OH    do.                   528                                                                               do. H  do. H   do.           H                --NH--CH.sub.3                                                                         do.                   529                                                                               do. H  do. H   do.           H                --NH--C.sub.6 H.sub.5                                                                  do.                   530                                                                               do. H  do. H   Br            H                --NH.sub.2                                                                             do.                   531                                                                               do. H  do. H   Cl            H                --NH.sub.2                                                                             do.                   532                                                                               do. H  do. H   CH.sub.3      H                --NH.sub.2                                                                             do.                   533                                                                               do. H  do. CH.sub.3                                                                           H             H                --NH.sub.2                                                                             do.                   534                                                                               do. H  do. OCH.sub.3                                                                          H             H                --NH.sub.2                                                                             do.                   535                                                                               do. H  do. H   OCH.sub.3     H                --NH.sub.                                                                              do.                   536                                                                               do. H  do. H   --NH--C.sub.2 H.sub.4 --F.sub.1                                                              H                H       do.                   537                                                                               do. H  do. H   --O--CO--CH.sub.2 --F.sub.1                                                                  H                H       do.                   538                                                                               do. H  do. H   CH.sub.2 --CH--CH.sub.2 --F.sub.1                                                            H                H       do.                                     |                                                                     --N∠OH                                                                   C.sub.2 H.sub.5                                              539                                                                               do. H  do. H   --SO.sub.2 N(CH.sub.3).sub.2                                                                 H                H       do.                   540                                                                               do. H  do. H   H             --COOC.sub.2 H.sub.4 --F.sub.1                                                                  OH      do.                   541                                                                               do. H  do. H   H             --COOCH.sub.3    OH      do.                   __________________________________________________________________________

Table XI sets forth the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##SPC5##

where B₁, B₂ and B₂₀ to B₂₃ have the meanings given them in Table XI. F may stand for any one of the radicals F₁ to F₂₃ in Table B. These groupings may be exchanged in any given dye for one of the other stated groupings.

                                      TABLE XI                                     __________________________________________________________________________     Exam-                                                                              B.sub.1                                                                             B.sub.2                                                                             B.sub.20                                                                           B.sub.21      B.sub.22         B.sub.23                                                                           Shade of dyeing           ple                                                  on Paper                  No.                                                                            __________________________________________________________________________     542 H    CH.sub.3                                                                            H   H             --CO--NH----CO--C.sub.2 H.sub.4 --F.sub.1                                                       OH  red                       543 H    H    H   H             do.              OH  do.                       544 CH.sub.3                                                                            CH.sub.3                                                                            H   H             do.              OH  do.                       545 H    OC.sub.2 H.sub.5                                                                    H   H             do.              OH  do.                       546 H    CH.sub.3                                                                            H   --NH--C.sub.2 H.sub.4 --F.sub.1                                                              H                H   do.                       547 H    H    H   do.           H                H   do.                       548 CH.sub.3                                                                            CH.sub.3                                                                            H   do.           H                H   do.                       549 H    OC.sub.2 H.sub.5                                                                    H   do.           H                H   do.                       550 H    CH.sub.3                                                                            H   OH            --CO--C.sub.2 H.sub.4 --F.sub.1                                                                 H   do.                                         CH.sub.3                                                                       |                                                   551 CH.sub.3                                                                            CH.sub.3                                                                            H   --SO.sub.2 --NH--CH--C.sub.3 H.sub.6 --F.sub.1                                               H                OH  do.                       552 H    CH.sub.3                                                                            H   H             --CO--NH--C.sub.2 H.sub.4 --F.sub.1                                                             OH  do.                       553 H    H    H   --O--CO--CH.sub.2 --F.sub.1                                                                  H                H   red                                         CH.sub.2 --CH--CH.sub.2 --F.sub.1                                              |                                                   554 H    CH.sub.3                                                                            H   --N∠OH  H                H   do.                                         C.sub.2 H.sub.5                                              554 H    OC.sub.2 H.sub.5                                                                    H   H             COOC.sub.2 H.sub.4 --F.sub.1                                                                    OH  do.                       __________________________________________________________________________

Table XII sets forth the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##EQU43## where B₁, B₂ and B₂₄ to B₂₆ have the meanings given them in Table XII. For F and the group --CH₂ --F the notes on Table X apply.

                                      TABLE XII                                    __________________________________________________________________________     Exam-                                                                          ple F     B.sub.1                                                                            B.sub.2                                                                             B.sub.24                                                                            B.sub.25       B.sub.26                                                                            Shade of dyeing                    No                                          on Paper                           __________________________________________________________________________     555-                                                                           568 F.sub.1 --F.sub.13                                                                   H   CH.sub.3                                                                            OH                  CH.sub.3                                                                            orange                             569 do.   H   H    OH   do.            do.  do.                                570 do.   CH.sub.3                                                                           CH.sub.3                                                                            OH   do.            do.  do.                                571 do.   H   OC.sub.2 H.sub.5                                                                    OH   do.            do.  do.                                572 do.   H   CH.sub.3                                                                            --NH.sub.2                                                                          do.            do.  do.                                573 do.   H   CH.sub.3                                                                            CH   --CH.sub.2 --CH.sub.2 --F.sub.1                                                                    do.                                574 do.   H   CH.sub.3                                                                            OH   --CH.sub.2 --F.sub.1                                                                          CH.sub.3                                                                            do.                                575 do.   CH.sub.3                                                                           CH.sub.2                                                                            OH   --OCH.sub.3    do.  do.                                576 do.   H   CH.sub.3                                                                            OH   --NH--CO--C.sub.2 H.sub.4 --F.sub.1                    577 do.   H   CH.sub.3                                                                            NH.sub.2            CH.sub.3                                                                            do.                                __________________________________________________________________________

Table XIII gives the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##EQU44## where B₁, B₂ and B₂₄ to B₂₆ have the meanings given them in Table XIII. For F the notes on Table XI apply.

                                      TABLE XIII                                   __________________________________________________________________________     Example                                                                             B.sub.1                                                                            B.sub.2                                                                              B.sub.24                                                                            B.sub.25        B.sub.26                                                                           Shade of dyeing                        No                                      on Paper                               __________________________________________________________________________     578  H   CH.sub.3                                                                             OH   --CH.sub.2 --CH.sub.2 --F.sub.1                                                                    orange                                 579  H   OC.sub.2 H.sub.5                                                                     OH   do.             do. do.                                    580  CH.sub.3                                                                           CH.sub.3                                                                             OH   do.             do. do.                                    581  H   H     OH   do.             do. do.                                    582  H   CH.sub.3                                                                             OH   --CH.sub.2 --F.sub.1                                                                           CH.sub.3                                                                           do.                                    583  CH.sub.3                                                                           CH.sub.3                                                                             OH   do.             do. do.                                    584  H   H     OH   do.             do. do.                                    585  H   OC.sub.2 H.sub.5                                                                     OH   do.             do. do.                                    586  H   CH.sub.3                                                                             OH   --NH--CO--C.sub.2 H.sub.4 --F.sub.1                                                            do. do.                                    587  H   H     OH   do.             do. do.                                    __________________________________________________________________________

Table XIV sets forth the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##EQU45## where B₁, B₂ and X have the meanings given them in the Table. For F and the group --CH₂ --F the notes on Table X apply.

                                      TABLE XIV                                    __________________________________________________________________________     Examp.                                                                             F     B.sub.1                                                                            B.sub.2                                                                              X              Shade of dyeing                             No                                 on Paper                                    __________________________________________________________________________     588 F.sub.1 -F.sub.13                                                                    H   CH.sub.3                                                                             --OH           yellow                                      589 do.   CH.sub.3                                                                           CH.sub.3                                                                             do.            do.                                         590 do.   H   OC.sub.2 H.sub.5                                                                     do.            do.                                         591 do.   H   H     do.            do.                                         592 do.   H   CH.sub.3                                                                             HO----CH.sub.3 do.                                         593 do.   H   CH.sub.3                                                                             HO--           do.                                                             |                                                                     CH.sub.3 CH.sub.3                                                              |                                                 594 do.   H   CH.sub.3                                                                             HO--OH         do.                                                             |                                                 595 do.   H   CH.sub.3                                                                             OH HO--        orange                                                          |                                                 596 do.   H   CH.sub.3                                                                             HO--OH         do.                                                             |                                                 597 do.   H   CH.sub.3                                                                             OH HO----CH.sub.2 OH                                                                          do. -       |                      598 do.   H   CH.sub.3                                                                             HO---- Cl      do.                                         599 do.   H   CH.sub.3                                                                             H.sub.2 N--    yellow                                                          OH                                                                             |                                                 600 do.   H   CH.sub.3                                                                             H.sub.2 N--    orange                                                          CH.sub.3                                                                       |                                                 601 do.   H   CH.sub.3                                                                             H.sub.2 N--    yellow                                                          CH.sub.3                                                                       |                                                 602 do.   H   CH.sub.3                                                                             H.sub.2 N--    do.                                                             |                                                                     OCH.sub.3                                                                      NH.sub.2                                                                       |                                                 603 do.   H   CH.sub.3                                                                             H.sub.2 N--    red                                                             NH                                                                             |                                                 604 do.   H   CH.sub.3                                                                             H.sub.2 N----Cl                                                                               do.                                                             NH.sub.2                                                                       |                                                 605 do.   H   CH.sub.3                                                                             H.sub.2 N----CH.sub.3                                                                         do.                                                             CH.sub.3                                                                       |                                                 606 do.   H   CH.sub.3                                                                             H.sub.2 N--    do.                                         607 do.   H   CH.sub.3             red-orange                                                      |                                                                     OH                                                         __________________________________________________________________________

Table XV sets forth the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##EQU46## where B₁, B₂ and B₂₇ to B₃₁ have the meanings given them in the Table. For F and the group --CH₂ --F the notes on Table X apply.

                                      TABLE XV                                     __________________________________________________________________________     Exam-                                                                              F     B.sub.1                                                                            B.sub.2                                                                             B.sub.27                                                                            B.sub.28   B.sub.29                                                                           B.sub.30                                                                              B.sub.31                                                                           Shade of dyeing              ple                                               on Paper                     No                                                                             __________________________________________________________________________     608 F.sub.1                                                                              H   CH.sub.3                                                                            OCH.sub.3                                                                           H          H   --CH.sub.2 --F                                                                        H   yellow                       609-                                                                           622 F.sub.2 -F.sub.13                                                                    H   do.  do.  H          H   do.    H   do.                          623 F.sub.1 -F.sub.13                                                                    H   H    do.  H          H   do.    H   do.                          624 do.   CH.sub.3                                                                           CH.sub.3                                                                            do.  H          H   do.    H   do.                          625 do.   H   OC.sub.2 H.sub.5                                                                    do.  H          H   do.    H   do.                          626 do.   H   CH.sub.3                                                                            H    H          H   H      H   do.                          627 do.   H   CH.sub.3                                                                            OCH.sub.3                                                                           H          H   OCH.sub.3                                                                             H   do.                          628 do.   H   CH.sub.3                                                                            OCH.sub.3                                                                           H          Cl  OCH.sub.3                                                                             H   do.                          629 do.   H   CH.sub.3                                                                            H    H          Cl  H      H   do.                          630 do.   H   CH.sub.3                                                                            OCH.sub.3                                                                           --CH.sub.2 --F.sub.1                                                                      H   --CH.sub.2 -- F.sub.1                                                                 H   do.                          631 do.   H   CH.sub.3                                                                            H    --NH--CO--CH.sub.2 --F.sub.1                                                              H   H      H   do.                          632 do.   H   CH.sub.3                                                                            CH.sub.3                                                                            H          H   H      H   do.                          633 do.   H   CH.sub.3                                                                            CH.sub.3                                                                            H          H   --CH.sub.2 --F.sub.1                                                                  H   do.                          634 do.   H   H    H    --NH--CO--CH.sub.2 --F.sub.1                                                              H   H      H   do.                          __________________________________________________________________________

Table XVI gives the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##EQU47## where B₁, B₂ and B₂₇ to B₃₁ have the meanings given them in the Table. For F the notes on Table XI apply.

                                      TABLE XVI                                    __________________________________________________________________________     Exam-                                                                              B.sub.1                                                                            B.sub.2                                                                             B.sub.27                                                                            B.sub.28    B.sub.29                                                                           B.sub.30                                                                              B.sub.31                                                                           Shade of dyeing                   ple                                          on paper                          No                                                                             __________________________________________________________________________     635 H   CH.sub.3                                                                            CH.sub.3                                                                            CH.sub.2 --F.sub.1                                                                         CH.sub.3                                                                           CH.sub.2 --F.sub.1                                                                    CH.sub.3                                                                           yellow                            636 H   H    CH.sub.3                                                                            do.         do. do.    do. do.                               637 CH.sub.3                                                                           CH.sub.3                                                                            do.  do.         do. do.    do. do.                               638 H   OC.sub.2 H.sub.5                                                                    do.  do.         do. do.    do. do.                               639 H   CH.sub.3                                                                            OCH.sub.3                                                                           H           H   --CH.sub.2 --F.sub.1                                                                  H   do.                               640 H   CH.sub.3                                                                            OCH.sub.3                                                                           CH.sub.2 --F.sub.1                                                                         H   --CH.sub.2 --F.sub.1                                                                  H   do.                               641 H   CH.sub.3                                                                            H    --NH--CO--CH.sub.2 --F.sub.1                                                               H   H      H   do.                               642 H   CH.sub.3                                                                            CH.sub.3                                                                            H           H   CH.sub.2 --F.sub.1                                                                    H   do.                               __________________________________________________________________________

Table XVII gives the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These dyes are of the formula ##EQU48## where B₁, B₂ and B₃₂ have the meanings given them in Table XVII. For F and the group --CH₂ --F the notes on Table X apply.

                  TABLE XVII                                                       ______________________________________                                                               19                 Shade                                                                          of                                    Ex   F        B.sub.1 B.sub.2                                                                               B.sub.32    dyeing                                No.                                      on                                                                             Paper                                 ______________________________________                                         643  F.sub.1 -F.sub.13                                                                       H       CH.sub.3                                                                              --OCH.sub.3 yellow                                644  do.      H       CH.sub.3                                                                              OC.sub.4 H.sub.9                                                                           do.                                   645  do.      H       CH.sub.3                                                                              --NH--CH.sub.3                                                                             do.                                   646  do.      H       CH.sub.3                                                                              --NH--C.sub.2 H.sub.4 --F.sub.1                                                            do.                                   647  do.      H       CH.sub.3                                                                              --NH--C.sub.2 H.sub. 4 --F.sub.1                                                           do.                                   648  do.      H       CH.sub.3                                                                              --NH.sub.2  do.                                   649  do.      H       CH.sub.3                                                                              --O--C.sub.2 H.sub.4 --F.sub.1                                                             do.                                   650  do.      H       CH.sub.3                                                                              --O--       do.                                   651  do.      H       CH.sub.3                                                                              --O----CH.sub.3                                                                            do.                                   652  do.      H       CH.sub.3                                                                              --O----O--CH.sub.3                                                                         do.                                                                CH.sub.3                                          653  do.      H       CH.sub.3                                                                              --O----OCH.sub.3                                                                           do.                                                                |                                                                     CH.sub.2 --F.sub.1                                654  do.      H       H      --OCH.sub.3 do.                                   655  do.      CH.sub.3                                                                               CH.sub.3                                                                              do.         do.                                   656  do.      H       OC.sub.2 H.sub.5                                                                      do.         do.                                   ______________________________________                                    

Table XVIII sets forth the structural composition of further dyes which can be produced and/or dyed in accordance with the present process. These are of the formula ##EQU49## where B₁, B₂ and B₃₂ have the meanings given them in Table XVIII. For F the notes on Table XI apply.

                  TABLE XVIII                                                      ______________________________________                                         Ex.  B.sub.1                                                                               B.sub.2 B.sub.32      Shade of dyeing                              No.                               on Paper                                     ______________________________________                                         657  H      CH.sub.3                                                                               --NH--C.sub.2 H.sub.4 -- F.sub.1                                                             yellow                                       658  H      H       do.           do.                                          659  CH.sub.3                                                                              CH.sub.3                                                                               do.           do.                                          660  H      OC.sub.2 H.sub.5                                                                       do.           do.                                          661  H      CH.sub.3                                                                               --O--C.sub.2 H.sub.4 -- F.sub.1                                                              do.                                          662  H      CH.sub.3                                                                               --O----OCH.sub.3                                                               |-     CH.sub.2 --F.sub.1                         663  H      H       do            do.                                          664  CH.sub.3                                                                              CH.sub.3                                                                               do            do.                                          ______________________________________                                    

The following dyes can be produced and dyed in accordance with the process of the present invention. They correspond to the formulae ##EQU50##

Formulae of representative dyes of the foregoing Examples are as follows: ##SPC6## 

Having thus disclosed the invention, what I claim is:
 1. A dye of the formula ##SPC7##wherein B₂ is hydrogen or methyl, M is ##EQU51## or ##EQU52## wherein each of R₈ and R₉ is independently methyl, ethyl or 2-hydroxyethyl, R₁₀ is methyl, ethyl, 2-hydroxyethyl or 2-carbamoylethyl, each of R₁₁ and R₁₂ is independently hydrogen, methyl, ethyl or 2-hydroxyethyl, and A⁻ is an anion, X is ##SPC8## wherein B₂₇ is hydrogen, methyl or methoxy, and m is 1 to
 3. 2. A dye according to claim 1wherein m is 1 to 2, inclusive.
 3. A dye according to claim 2wherein each --CH₂ --M is attached to a 2'- or 7-position of the benzothiazolylphenyl group.
 4. A dye according to claim 2 having the formula ##SPC9##wherein B₂ is hydrogen or methyl, R₁₁ is hydrogen, methyl, ethyl or 2-hydroxyethyl, R₁₂ is hydrogen, methyl, ethyl or 2-hydroxyethyl, X is ##SPC10##wherein B₂₇ is hydrogen, methyl or methoxy, and q is 1 to
 2. 5. A dye according to claim 4wherein each ##EQU53## is attached to a 2' or 7-position of the benzothiazolylphenyl group.
 6. A dye according to claim 2 having the formula ##SPC11##wherein B₂ is hydrogen or methyl, each of R₈ and R₉ is independently methyl, ethyl or 2-hydroxyethyl, R₁₀ is methyl, ethyl, 2-hydroxyethyl or 2-carbamoylethyl, X is ##SPC12##wherein B₂₇ is hydrogen, methyl or methoxy, q is 1 to 2, and A⁻ is an anion.
 7. A dye according to claim 6wherein each ##EQU54## is attached to a 2'- or 7-position of the benzothiazolylphenyl group.
 8. A dye according to claim 6 having the formula ##SPC13##wherein X is ##SPC14##
 9. A dye according to claim 8wherein each ##EQU55## is attached to a 2' or 7-position of the benzothiazolylphenyl group.
 10. A dye according to claim 8 having the formula ##SPC15##
 11. A dye according to claim 8 having the formula ##EQU56##
 12. A dye according to claim 8 having the formula ##SPC16##
 13. The dye according to claim 1 having the formula ##SPC17##
 14. A dye according to claim 1 having the formula ##SPC18## 